Arylbis (perfluoroalkylsulfonyl)methane and metallic salt thereof, and methods for producing the same

ABSTRACT

The present invention provides a method for producing various types of arylbis(perfluoroalkylsulfonyl)methane having a bulky aryl group and an electron-accepting aryl group in which synthesis was conventionally considered to be difficult, at high efficiency; a novel arylbis(perfluoroalkylsulfonyl)methane that can be widely applied to asymmertric catalyst, various types of functional materials and the like; and a metallic salt thereof. In addition, excellent catalysts are also provided. An aryl halomethane is reacted with a sodium trifluoromethane sulfinate, the arylmethyl triflone produced thereby is reacted with a t-BuLi and the like, the lithium salt of the arylmethyl triflone obtained is reacted with a trifluoromethane sulfonic acid anhydride, and an arylbis (trifluoromethylsulfony)methane such as pentafluorophenylbis(triflyl)methane, {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane and the like are obtained at a high yield.

TECHNICAL FIELD

The present invention relates to a method for producingarylbis(perfluoroalkylsulfonyl)methane such as arylbis(triflyl)methaneand the like, by using sodium trifluoromethane sulfinate andtrifluoromethane sulfonic acid anhydride as an electrophilic reactantused as a triflyl source, and a novelarylbis(perfluoroalkylsulfonyl)methane such aspentafluorophenylbis(triflyl)methane,{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane andthe like obtained from said method.

Moreover, the present invention relates to a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane, that is, a metallicarylbis(perfluoroalkylsulfonyl)methide, a method for producing saidcompound, catalysts such as Lewis acid catalyst which comprises saidcompound as an active ingredient, and a method for synthesizing organiccompounds by using said catalysts.

BACKGROUND ART

Trifluoromethane sulfonyl (—SO₂CF₃; triflyl, Tf) group is known as oneof the strongest electron-accepting group, which has an action toincrease the protonic acidity of its a position (J. Am. Chem. Soc. 96,2275, 1974; Synthesis, 691, 1997; J. Fluorine Chem. 66, 301, 1994). Forexample, bis(triflyl)methane (CH₂Tf₂; pK_(a)(H₂O)=−1) (J. Am. Chem. Soc.106, 1510, 1984) and phenylbis(triflyl)methane (PhCHTf₂;pK_(a)(MeCN)=7.83) (J. Org. Chem. 63, 7868, 1998) are strong acids thatdo not have the ability to oxidize. The inherent acidity ΔG_(acid) (ingas condition) estimated by Koppel et al. is as follows (J. Am. Chem.Soc. 116, 3047, 1994): MeSO₃H (315.0)<CH₂Tf₂ (310.5)<PhCHTf₂(310.3)<TfOH (299.5)<NHTf₂ (291.8)<CHTf₃ (289.0). These volatilecrystalline solids are known to serve as a reactant when preparing acationic organometallic dihydrido by protonating an organometallichydrido (J. Am. Chem. Soc. 106, 1510, 1984; J. Chem. Soc., Chem. Commun.1675, 1987; Inorg. Chem. 27, 1593, 1988; Inorg. Chem. 27, 2473, 1988;Organometallics 9, 1290, 1990). Based on these facts, it is expectedthat the steric and electronic effects of the aromatic group in thearylbis(triflyl)methane such as phenylbis(triflyl)methane and the likementioned above, have a great effect on its Broensted acidity and theproperty of their organometallic complex.

Heretofore, two methods have been known as a method for synthesizingthephenylbis(triflyl)methane mentioned above (J. Org. Chem. 38, 3358, 1973;Heteroatom Chem. 5, 9, 1994; J. Fluorine Chem. 64, 47, 1993; J. FluorineChem. 106, 139, 2000). One of the methods is a method wherein benzylmagnesium chloride is reacted with triflyl fluoride to synthesizephenylbis(triflyl)methane (40% yield) (J. Org. Chem. 38, 3358, 1973),and the other method is a method wherein light response betweeniodobenzene bis(triflylmethide) and benzene is conducted (61% yield)(Heteroatom Chem. 5, 9,1994). The former requires a triflyl fluoride gas(bp=−21° C.) which is difficult to obtain, as a triflyl source, and thelatter requires an excessive amount of benzene, a reactant, as asolvent. Moreover, in the case of the latter, arylbis(triflyl)methane isnot formed when light response is conducted with allene, which has anelectron-accepting group such as fluorobenzene.

Meanwhile, a method for synthesizing benzyl triflone has been reportedby Hendrickson et al. (J. Am. Chem. Soc. 96, 2275, 1974; Synthesis, 691,1997; J. Fluorine Chem. 66, 301, 1994). However, there was a problemthat arylmethyl triflone could not be synthesized at a high yield whenthe aromatic group is an electron-accepting group and is inactivated(Synthesis, 691, 1997).

In addition, Lewis acid catalyst is known to be the most widely usedcatalyst in the aspect of organic synthesis. This Lewis acid catalystassociates with a specific functional group of an organic compound,forms a complex, and can be made to conduct a particular response only.The one that accepts an electron pair from which it reacts with isreferred to as Lewis acid. Organic compounds generally have a functionalgroup, and the functional group is usually a Lewis base, which attractsmutually with Lewis acid. The Lewis acid catalyst designed in thismanner forms a complex with the functional group of the organiccompound, and leads directly to the desired reaction. Due to this point,Lewis acid catalyst is also compared to an artificial enzyme. However,the reactivity and selectivity of the conventional Lewis acid catalystwas not so high compared to when enzyme was used, and was notsufficient. Therefore, a Lewis acid catalyst that has an excellentselectivity and reactivity, and further capable of reacting under warmcondition has been required.

Heretofore, a Lewis acid catalyst comprised of a compound shown by ageneral formula M[RfSO₂—N—SO₂Rf′]_(n) or M[RfSO₂—N—SO₂Rf′]_(n).mH₂O(wherein Rf and Rf′ represent a perfluoroalkyl group having 1 to 8carbon atoms, M represents an element selected from alkaline metal,alkaline earth metal, transition metal, rare earth, aluminum, gallium,iridium, thallium, silicon, germanium, tin, lead, arsenic, antimony,bismuth, selenium and tellurium, n represents an integer of the samenumber as the valence of the corresponding metal, and m represents anatural number from 0.5 to 20) (Japanese Laid Open Patent ApplicationNo. 07-246338), and a Lewis acid catalyst shown by the followingformula,

-   -   [wherein X represents —N(Tf¹)Tf² [wherein Tf¹ represents        —SO₂Rf¹, Tf² represents —SO₂Rf² (wherein each of Rf¹ and Rf²        independently represents a fluorine atom or a perfluoroalkyl        group)], R¹ represents a substituted or unsubstituted        cyclopentadienyl group, —OR³ or —N(Tf³)R⁴, R² represents a        substituted or unsubstituted cyclopentadienyl group, —OR⁵ or        —N(Tf⁴)R⁶ [wherein Tf³ represents —SO₂Rf³, Tf⁴ represents        —SO₂Rf⁴ (wherein each of Rf³ and Rf⁴ independently represents a        fluorine atom or a perfluoroalkyl group), each of R³, R⁴, R⁵ and        R⁶ independently represents a lower alkyl group, or, R³ and R⁵,        R³ and R⁶, R⁴ and R⁵ or R⁴ and R⁶ form together a bivalent        group], M represents an element selected from alkaline earth        metal, rare earth element, transition metal, boron, aluminum,        gallium, indium, thallium, silicon, germanium, tin, lead,        arsenic, antimony, bismuth, selenium or tellurium, n represents        an integer of valence −2 of the corresponding M, and has at        least one of −N(Tf¹)Tf², —N(Tf³)R⁴ or —N(Tf⁴)R⁶] (Japanese Laid        Open Patent Application No. 09-57110), have been known as Lewis        acid catalysts.

Aside from the examples mentioned above, there have been disclosures ofhighly active acid catalysts, including a highly active Lewis acidcatalyst that can be used under the coexistence of water, comprising ametallic halide shown by a general formula M⁺(X₁ ⁻)q (wherein Mrepresents at least one metal selected from a group comprising elementsfrom IIIA family to VB family of the periodic table, X₁ represents ahalogen atom, and q represents an integer that is identical to thevalence number of M) and a quaternary salt type anion exchange resin(Japanese Laid Open Patent Application No. 09-262479), and an acidcatalyst comprising a metallic salt oftris(perfluoroalkylsulfonyl)methide shown by the following formula[(RfSO₂)₃C]_(n)M₂ (however, Rf represents a perfluoroalkyl group havingone or more carbon atoms, M₂ represents an element selected fromalkaline metal, alkaline earth metal, transition metal including rareearth, zinc, cadmium, aluminum, gallium, indium, thallium, silicon,germanium, tin, lead, arsenic, antimony, bismuth, selenium or tellurium.n represents an integer of the same number as the valence of M₂)(Japanese Laid Open Patent Application No. 2000-219692).

Heretofore, TfOH, Tf₂NH, Tf₂CH₂ and Tf₃CH have already been known as anorganic acid having a triflyl group. However, chemical modification tothese molecules is not easy and therefore, it is difficult to make themolecules have a novel function. Due to this reason, they were notconsidered to be an appropriate material when producing pharmaceuticals,agricultural chemicals, asymmetric catalysts, various types offunctional materials and the like. Moreover, recently, the developmentof a catalyst capable of easily conducting asymmetric synthesis, whichis called chiral technology or chiral industry in the field of medicineand agricultural chemical, is expected for the development andapplication of pharmaceuticals, agricultural chemicals, various types offunctional materials and the like.

The object of the present invention is to provide: a method wherein anarylbis(perfluoroalkylsulfonyl)methane such as the various types ofarylbis(triflyl)methane and the like having a bulky aryl group and anelectron-accepting aryl group in which its synthesis was conventionallyconsidered to be difficult, is produced easily and highly efficiently; anovel arylbis(perfluoroalkylsulfonyl)methane such aspentafluorophenylbis(triflyl)methane,{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane andthe like, which can be widely applied to asymmetric catalyst, varioustypes of functional materials and the like; a method for producing ametallic salt of arylbis(perfluoroalkylsulfonyl)methane that hasexcellent selectivity and reactivity, can further react under warmcondition, and introduce various types of aryl groups, that is, metallicarylbis(perfluoroalkylsulfonyl)methide, wherein saidarylbis(perfluoroalkylsulfonyl)methane is used,; a metallicarylbis(perfluoroalkylsulfonyl)methide obtained by said method;catalysts such as Lewis acid catalyst and the like comprised of saidcompound; and a method for synthesizing organic compounds by using saidcatalysts.

DISCLOSURE OF THE INVENTION

The present inventors have found out thatarylbis(trifluoromethylsulfonyl)methane can be produced at a high yieldby the following steps: an easily obtainable aryl halomethane was usedas a starting material; sodium trifluoromethane sulfinate (TfNa) wasused as an electrophilic reactant as a triflyl source; heating underreflux was conducted with the use of propionitrile as a solvent underthe presence of 10 mol % tetrabutyl ammonium iodide catalyst to conductnucleophilic substitution; arylmethyl trifluoromethylsulfone wasproduced at a high yield; and 2.2 equivalent weight of tert-butyllithium (t-BuLi) and 1.1 equivalent weight of trifluoromethane sulfonicacid anhydride (Tf₂O) were sequentially added to the arylmethyltrifluoromethylsulfone produced. Thus, the present invention had beencompleted.

Further, the present inventors conducted a keen study to elucidate theobject mentioned above. In the same manner as the method describedabove, TfNa and Tf₂O were used to synthesizepentafluorophenylbis(triflyl)methane; thepentafluorophenylbis(triflyl)methane obtained was subjected to heatingunder reflux with scandium oxide (Sc₂O₃) in water to produce scandium(III) pentafluorophenylbis(triflyl); said compound was used as a Lewisacid catalyst for benzoylation reaction with menthol and benzoic acidanhydride, and Diels-Alder reaction of methacrolein withcyclopentadiene; and it was confirmed that said compound has a bettercatalyst activity than the existing Lewis acids. Thus, the presentinvention has been completed.

The present invention relates to anarylbis(perfluoroalkylsulfonyl)methane represented by the followinggeneral formula [1]

-   -   (wherein R¹ shows a substituted or unsubstituted aryl group        (however, phenyl group is excluded), Rf¹ and Rf² are independent        to each other and show a perfluoroalkyl group) (claim 1); the        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [1] according to claim 1, wherein R¹ is a        naphthyl group, a 2,4,6-trimethylphenyl group, a        4-(trifluoromethyl)phenyl group, a        3,5-bis(trifluoromethyl)phenyl group, a pentafluorophenyl group        or a perfluorobiphenyl group (claim 2); the        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [1] according to claim 1, wherein Rf¹ and Rf²        are both a trifluoromethyl group (claim 3); a        pentafluorophenylbis(trifluoromethylsulfonyl)methane represented        by formula [2]    -   or a para position substituent thereof (claim 4); and a        {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane        represented by formula [3]    -   or a 4′ position substituent thereof (claim 5).

Further, the present invention relates to a method for producing anarylbis(perfluoroalkylsulfonyl)methane represented by general formula[4]

-   -   (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group),wherein an aryl halomethane is reacted with a        perfluoroalkyl sulfinate, an arylmethylperfluoroalkylsulfone        produced is reacted with a deprotonation agent comprised of an        organic metal or a metallic salt, and a metallic salt of        arylmethylperfluoroalkylsulfone obtained is reacted with a        perfluoroalkyl sulfonic acid anhydride (claim 6); the method for        producing the arylbis(perfluoroalkylsulfonyl)methane represented        by the general formula [4] according to claim 6, wherein the        aryl halomethane is reacted with the perfluoroalkyl sulfinate by        heating under reflux using a solvent with or without the        presence of a catalyst (claim 7) ; the method for producing the        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [4] according to claim 7, wherein a tetrabutyl        ammonium iodide is used as the catalyst (claim 8); the method        for producing the arylbis(perfluoroalkylsulfonyl)methane        represented by the general formula [4] according to claim 7,        wherein a propionitrile is used as the solvent (claim 9); the        method for producing the arylbis(perfluoroalkylsulfonyl)methane        represented by the general formula [4] according to claim 6,        wherein a deprotonation agent comprised of an organic metal or a        metallic salt having an equivalent weight of 1.7 to 2.4 is        reacted to the arylmethylperfluoroalkylsulfone (claim 10); the        method for producing the arylbis(perfluoroalkylsulfonyl)methane        represented by the general formula [4] according to claim 6,        wherein the aryl halomethane is a benzyl bromide, a        2-bromomethylnaphthalene, a 1-chloromethylnaphthalene, a        2,4,6-trimethylphenylmethylchloride, a        4-(trifluoromethyl)phenylmethylbromide, a        3,5-bis(trifluoromethyl)phenylmethylbromide, a        pentafluorophenylmethylbromide or a        4-(bromomethyl)perfluorobiphenyl (claim 11); the method for        producing the arylbis(perfluoroalkylsulfonyl)methane represented        by the general formula [4] according to claim 6, wherein the        perfluoroalkyl sulfinate is an alkaline metallic salt of        trifluoromethane sulfinic acid (claim 12); the method for        producing the arylbis(perfluoroalkylsulfonyl)methane represented        by the general formula [4] according to claim 6, wherein the        metallic salt of arylmethylperfluoroalkylsulfone is a lithium        salt or a magnesium salt of arylmethylperfluoroalkylsulfone        (claim 13); the method for producing the        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [4] according to claim 6, wherein the        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [4] is an        arylbis(trifluoromethylsulfonyl)methane represented by general        formula [5]    -   (wherein R² shows a substituted or unsubstituted aryl group)        (claim 14); the method for producing the        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [4] according to claim 14, wherein the        arylbis(trifluoromethylsulfonyl)methane represented by the        general formula [5] is a        pentafluorophenylbis(trifluoromethylsulfonyl)methane represented        by formula [2]    -   (claim 15); and the method for producing the        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [4] according to claim 14, wherein the        arylbis(trifluoromethylsulfonyl)methane represented by the        general formula [5] is a        {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane        represented by formula [3]    -   (claim 16).

The present invention relates to a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[6]

-   -   (wherein R² shows a substituted or unsubstituted aryl group        (however, phenyl group is excluded), Rf¹ and Rf² are independent        to each other and show a perfluoroalkyl group, M shows any one        of the elements selected from alkaline metallic element,        alkaline earth metallic element, transition metallic element,        boron, silicon, aluminum, tin, zinc or bismuth, n shows a        numeric value equal to the valence of M element) (claim 17); the        metallic salt of arylbis(perfluoroalkylsulfonyl)methane        according to claim 17, wherein the transition metallic element        is any one of the metallic elements selected from scandium,        yttrium, lanthanoid, copper, silver, titanium, zirconium or        hafnium (claim 18); the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 17,        wherein Rf¹ and Rf² are both a trifluoromethyl group (claim 19);        the metallic salt of arylbis(perfluoroalkylsulfonyl)methane        according to claim 17, wherein R² is a phenyl group, a naphthyl        group, a 2,4,6-trimethylphenyl group, a        4-(trifluoromethyl)phenyl group, a        3,5-bis(trifluoromethyl)phenyl group, a pentafluorophenyl group        or a perfluorobiphenyl group (claim 20); the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 17,        wherein the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane is a metallic salt of        phenylbis(triflyl)methane, a metallic salt of        2-naphthylbis(triflyl)methane, a metallic salt of        1-naphthylbis(triflyl)methane, a metallic salt of        2,4,6-trimethylphenylbis(triflyl)methane, a metallic salt of        4-(trifluoromethyl)phenylbis(triflyl)methane, a metallic salt of        3,5-bis(trifluoromethyl)phenylbis(triflyl)methane, a metallic        salt of pentafluorophenylbis(triflyl)methane or a metallic salt        of        {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane        (claim 21); the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 21,        wherein the metallic salt of        pentafluorophenylbis(triflyl)methane is a scandium (III)        pentafluorophenylbis(triflyl)methide or a lithium        pentafluorophenylbis(triflyl)methide (claim 22); and the        metallic salt of arylbis(perfluoroalkylsulfonyl)methane        according to claim 21, wherein the metallic salt of        {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane        is a scandium (III)        {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methide        or a lithium        {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methide        (claim 23).

Further, the present invention relates to a method for producing ametallic salt of arylbis(perfluoroalkylsulfonyl)methane, wherein themethod is a method for producing a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[6]

-   -   (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group, M shows any one of the elements selected from alkaline        metallic element, alkaline earth metallic element, transition        metallic element, boron, silicon, aluminum, tin, zinc or        bismuth, n shows a numeric value equal to the valence of M        element)    -   wherein an arylbis(perfluoroalkylsulfonyl)methane represented by        general formula [4]    -   (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group)    -   is neutralized with a hydroxide of a metal (claim 24); the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 24,        wherein the hydroxide of the metal is a hydroxide of a metal        selected from alkaline metal or alkaline earth metal (claim 25);        the method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 24,        wherein the arylbis(perfluoroalkylsulfonyl)methane represented        by the general formula [4] is used, which is obtained by        reacting an aryl halomethane with a perfluoroalkyl sulfinate,        followed by reacting an arylmethylperfluoroalkylsulfone produced        with a deprotonation agent comprised of an organic metal or an        metallic salt, and a metallic salt of        arylmethylperfluoroalkylsulfone obtained is reacted with a        perfluoroalkyl sulfonic acid anhydride (claim 26); the method        for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 26,        wherein the aryl halomethane is reacted with the perfluoroalkyl        sulfinate by heating under reflux using a solvent with or        without the presence of a catalyst (claim 27); the method for        producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 27,        wherein a tetrabutyl ammonium iodide is used as the catalyst        (claim 28); the method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 27,        wherein a propionitrile is used as the solvent (claim 29); the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 26,        wherein the perfluoroalkyl sulfinate is an alkaline metallic        salt of trifluoromethane sulfinic acid (claim 30); the method        for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 26,        wherein the metallic salt of arylmethylperfluoroalkylsulfone is        a lithium salt or a magnesium salt of        arylmethylperfluoroalkylsulfone (claim 31); a method for        producing a metallic salt of        arylbis(perfluoroalkylsulfonyl)methane, wherein the method is a        method for producing a metallic salt of        arylbis(perfluoroalkylsulfonyl)methane represented by general        formula [6],    -   (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group, M shows any one of the elements selected from alkaline        metallic element, alkaline earth metallic element, transition        metallic element, boron, silicon, aluminum, tin, zinc or        bismuth, n shows a numeric value equal to the valence of M        element)    -   wherein an arylbis(perfluoroalkylsulfonyl)methane represented by        general formula [4]    -   (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group)    -   is reacted with a salt or an oxide of transition metal by        heating under reflux (claim 32); the method for producing the        metallic salt of arylbis(perfluoroalkylsulfonyl)methane        according to claim 32, wherein the salt or the oxide of        transition metal is a lanthanoid metallic salt or a scandium        oxide (claim 33); the method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 32,        wherein the arylbis(perfluoroalkylsulfonyl)methane represented        by the general formula [4] is used, which is obtained by        reacting an aryl halomethane with a perfluoroalkyl sulfinate,        followed by reacting an arylmethylperfluoroalkylsulfone produced        with a deprotonation agent comprised of an organic metal or a        metallic salt, and ametallic salt of        arylmethylperfluoroalkylsulfone obtained is reacted with a        perfluoroalkyl sulfonic acid anhydride (claim 34); the method        for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 34,        wherein the aryl halomethane is reacted with the perfluoroalkyl        sulfinate by heating under reflux using a solvent with or        without the presence of a catalyst (claim 35); the method for        producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 35,        wherein a tetrabutyl ammonium iodide is used as the catalyst        (claim 36); the method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 35,        wherein a propionitrile is used as the solvent (claim 37); the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 34,        wherein the perfluoroalkyl sulfinate is an alkaline metallic        salt of trifluoromethane sulfinic acid (claim 38); and the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 34,        wherein the metallic salt of arylmethylperfluoroalkylsulfone is        a lithium salt or a magnesium salt of        arylmethylperfluoroalkylsulfone (claim 39).

The present invention also relates to a method for producing a metallicsalt of arylbis(perfluoroalkylsulfonyl)methane, wherein the method is amethod for producing a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[6]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group, M showsany one of the elements selected from alkaline metallic element,alkaline earth metallic element, transition metallic element, boron,silicon, aluminum, tin, zinc or bismuth, n shows a numeric value equalto the valence of M element)

-   -   wherein a metallic salt of        arylbis(perfluoroalkylsulfonyl)methane represented by general        formula [4]    -   (wherein R² shows a substituted or unsubstituted aryl group. Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group)    -   is reacted with a halide of a metal having different metal        species (claim 40); the method for producing the metallic salt        of arylbis(perfluoroalkylsulfonyl)methane according to claim 40,        wherein the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane represented by the        general formula [6] is a silver salt of        arylbis(perfluoroalkylsulfonyl)methane (claim 41); the method        for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 40,        wherein the arylbis(perfluoroalkylsulfonyl)methane represented        by the general formula [4] is used, which is obtained by        reacting an aryl halomethane with a perfluoroalkyl sulfinate,        followed by reacting an arylmethylperfluoroalkylsulfone produced        with a deprotonation agent comprised of an organic metal or a        metallic salt, and a metallic salt of        arylmethylperfluoroalkylsulfone obtained is reacted with a        perfluoroalkyl sulfonic acid anhydride (claim 42); the method        for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 42,        wherein the aryl halomethane is reacted with the perfluoroalkyl        sulfinate by heating under reflux using a solvent with or        without the presence of a catalyst (claim 43); the method for        producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 43,        wherein a tetrabutyl ammonium iodide is used as the catalyst        (claim 44); the method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 43,        wherein a propionitrile is used as the solvent (claim 45); the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 42,        wherein the perfluoroalkyl sulfinate is an alkaline metallic        salt of trifluoromethane sulfinic acid (claim 46); and the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 42,        wherein the metallic salt of arylmethylperfluoroalkylsulfone is        a lithium salt or a magnesium salt of        arylmethylperfluoroalkylsulfone (claim 47).

Further, the present invention relates to a method for producing ametallic salt of arylbis(perfluoroalkylsulfonyl)methane, wherein themethod is a method for producing a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[6]

-   -   (wherein R² shows a substituted or unsubstituted aryl group        (however, phenyl group is excluded), Rf¹ and Rf² are independent        to each other and show a perfluoroalkyl group, M shows any one        of the elements selected from alkaline metallic element,        alkaline earth metallic element, transition metallic element,        boron, silicon, aluminum, tin, zinc or bismuth, n shows a        numeric value equal to the valence of M element)    -   wherein an arylbis(perfluoroalkylsulfonyl)methane represented by        general formula [4]        (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group)    -   is reacted with a silver carbonate under shade (claim 48); the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 48,        wherein the arylbis(perfluoroalkylsulfonyl)methane represented        by the general formula [4] is used, which is obtained by        reacting an aryl halomethane with a perfluoroalkyl sulfinate,        followed by reacting an arylmethylperfluoroalkylsulfone produced        with a deprotonation agent comprised of an organic metal or a        metallic salt, and a metallic salt of        arylmethylperfluoroalkylsulfone obtained is reacted with a        perfluoroalkyl sulfonic acid anhydride (claim 49); the method        for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 49,        wherein the aryl halomethane is reacted with the perfluoroalkyl        sulfinate by heating under reflux using a solvent with or        without the presence of a catalyst (claim 50); the method for        producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 50,        wherein a tetrabutyl ammonium iodide is used as the catalyst        (claim 51); the method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 50,        wherein a propionitrile is used as the solvent (claim 52); the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 49,        wherein the perfluoroalkyl sulfinate is an alkaline metallic        salt of trifluoromethane sulfinic acid (claim 53); and the        method for producing the metallic salt of        arylbis(perfluoroalkylsulfonyl)methane according to claim 49,        wherein the metallic salt of arylmethylperfluoroalkylsulfone is        a lithium salt or a magnesium salt of        arylmethylperfluoroalkylsulfone (claim 54).

Moreover, the present invention relates to a catalyst having a metallicsalt of arylbis(perfluoroalkylsulfonyl)methane represented by generalformula [6]

-   -   (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group, M shows any one of the elements selected from alkaline        metallic element, alkaline earth metallic element, transition        metallic element, boron, silicon, aluminum, tin, zinc or        bismuth, n shows a numeric value equal to the valence of M        element)    -   as an active ingredient (claim 55); and the catalyst according        to claim 55, wherein the catalyst is a Lewis acid catalyst        (claim 56).

Still further, the present invention relates to a method forsynthesizing an organic compound wherein the method is a method forsynthesizing an organic compound by using a catalyst having a metallicsalt of arylbis(perfluoroalkylsulfonyl)methane represented by generalformula [6]

-   -   (wherein R² shows a substituted or unsubstituted aryl group, Rf¹        and Rf² are independent to each other and show a perfluoroalkyl        group, M shows any one of the elements selected from alkaline        metallic element, alkaline earth metallic element, transition        metallic element, boron, silicon, aluminum, tin, zinc or        bismuth, n shows a numeric value equal to the valence of M        element)    -   as an active ingredient, and catalytic reaction is conducted        under the presence of said catalyst in a solvent (claim 57); and        the method for synthesizing an organic compound according to        claim 57, wherein the catalytic reaction is a benzoylation        reaction, a Diels-Alder reaction, an aldol-type reaction, a        Friedel-Crafts reaction, a Mannich reaction, a glycosilation        reaction, an esterification reaction, an ene reaction, a        cationic polymerization reaction or an allylation reaction        (claim 58).

BEST MODE OF CARRYING OUT THE INVENTION

In the arylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [1] (wherein R¹ shows a substituted or unsubstituted aryl group(however, phenyl group is excluded), Rf¹ and Rf² are independent to eachother and show a perfluoroalkyl group) of the present invention,examples of R¹ include an aryl group having a substituent such as aphenyl group, a naphthyl group, a biphenyl group and the like having asubstituent, and an unsubstituted aryl group excluding phenyl group suchas an α-naphthyl group, a β-naphthyl group, a biphenyl group and thelike. Examples of the substituent for this case include a C1-C4 alkylgroup such as methyl group and the like, a halogenated C1-C4 alkyl groupsuch as trifluoromethyl group and the like, a halogen atom such asfluorine and the like, an alkoxy group, a sulfonyl group, an amino groupand the like. Specific examples of said R¹ include a naphthyl group, a2,4,6-trimethylphenyl group, a 4-(trifluoromethyl)phenyl group, a3,5-bis(trifluoromethyl)phenyl group, a pentafluorophenyl group, ap-tolyl group, an m-tolyl group, a mesityl group, a xylyl group, abiphenyl group, a perfluorobiphenyl group, a p-chlorophenyl group, ano-chlorophenyl group and the like.

There is no particular limitation to the method for producingarylbis(perfluoroalkylsulfonyl) methane represented by the generalformula [4] (wherein R² shows a substituted or unsubstituted aryl group,Rf¹ and Rf² are independent to each other and show a perfluoroalkylgroup) of the present invention, as long as it is a method wherein anaryl halomethane is reacted with a perfluoroalkyl sulfinate, thearylmethylperfluoroalkylsulfone produced is reacted with a deprotonationagent comprised of an organic metal or a metallic salt, and the metallicsalt of arylmethylperfluoroalkylsulfone obtained is reacted with ananhydrous perfluoroalkyl sulfonic acid. Moreover, the method forproducing an arylbis(perfluoroalkylsulfonyl)methane obtained by furtherreacting the arylbis(perfluoroalkylsulfonyl)methane obtained by themethod mentioned above with alkyl anion such as alkyl lithium, alkoxyanion such as alkoxy lithium and the like, is also included in themethod of the present invention. Examples of R² in the formula [4]mentioned above include an aryl group such as a substituted orunsubstituted phenyl group, naphthyl group, biphenyl group and the like.Examples of the substituent for this case include a C1-C4 alkyl groupsuch as methyl group and the like, a halogenated C1-C4 alkyl group suchas trifluoromethyl group and the like, a halogen atom such as fluorineand the like, an alkoxy group, a sulfonyl group, an amino group and thelike. Specific examples of said R² include a phenyl group, a naphthylgroup, a 2,4,6-trimethylphenyl group, a 4-(trifluoromethyl)phenyl group,a 3,5-bis(trifluoromethyl)phenyl group, a pentafluorophenyl group, ap-tolyl group, a m-tolyl group, a mesityl group, a xylyl group, abiphenyl group, a perfluorobiphenyl group, a p-chlorophenyl group, ano-chlorophenyl group and the like.

The Rf¹ and Rf² in the general formulae [1] and [4] mentioned above showa perfluoroalkyl group that may be the same or different from eachother, preferably a C1-C8 perfluoroalkyl group. Specific examples of—SO₂Rf¹ and —SO₂Rf² containing these Rf¹ and Rf² include atrifluoromethylsulfonyl group, a perfluoroethylsulfonyl group, aperfluoropropylsulfonyl group, a perfluoroisopropylsulfonyl group, aperfluorobutylsulfonyl group, a perfluoroisobutylsulfonyl group, aperfluoropentylsulfonyl group, a perfluoroisopentylsulfonyl group, aperfluoroneopentylsulfonyl group and the like.

Specific examples of the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [1] of the present invention are, forexample, a 2-naphthylbis(triflyl)methane, a1-naphthylbis(triflyl)methane, a2,4,6-trimethylphenylbis(triflyl)methane, a4-(trifluoromethyl)phenylbis(triflyl)methane, a3,5-bis(trifluoromethyl)phenylbis(triflyl)methane, thepentafluorophenylbis(triflyl)methane represented by the formula [2], the{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methanerepresented by the formula [3] and the like. However, the examples arenot limited to these. Further, examples of the compound of the presentinvention include: a para position substituent of thepentafluorophenylbis(triflyl)methane represented by the formula [2]mentioned above, for example, a para position alkyl substituent such asa p-phenyl-2,3,5,6-tetrafluorophenyl-bis(triflyl) and the like, a paraposition alkoxy substituent such asp-hexanoxy-2,3,5,6-tetrafluorophenyl-bis(triflyl) and the like; a 4′position substituent of the{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methanerepresented by the formula [3], for example, a 4′ position alkylsubstituent such as a[4-(4-phenyl-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluorophenyl]bis(triflyl)and the like, a 4′ position alkoxy substituent such as a[4-(4-hexanoxy-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluorophenyl]bis(triflyl)methaneand the like, etc.

A specific example of the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [4] in the method for producing thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] of the present invention is thearylbis(trifluoromethylsulfonyl)methane represented by the generalformula [5] (wherein R² shows the aforementioned aryl group), whichincludes, for example, a phenylbis (triflyl)methane, a2-naphthylbis(triflyl)methane, a 1-naphthylbis(triflyl)methane, a2,4,6-trimethylphenylbis(triflyl)methane, a4-(trifluoromethyl)phenylbis(triflyl)methane, a3,5-bis(trifluoromethyl)phenylbis(triflyl)methane, thepentafluorophenylbis(triflyl)methane represented by the formula [2], the{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methanerepresented by the formula [3], and the like. However, the examples arenot limited to these.

There is no particular limitation to the aryl halomethane used in themethod for producing the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [4] of the present invention, as longas it is a methane substituted by a substituted or unsubstituted arylgroup and a halogen atom. Specific examples include a benzyl bromide, a2-bromomethylnaphthalene, a 1-chloromethylnaphthalene, a2,4,6-trimethylphenylmethylchloride, a4-(trifluoromethyl)phenylmethylbromide, a3,5-bis(trifluoromethyl)phenylmethylbromide, apentafluorophenylmethylbromide, a4-(bromomethyl)perfluorobiphenyl(perfluorobiphenylmethylbromide) and thelike.

A preferable example of the perfluoroalkyl sulfinate used in the methodfor producing the arylbis(perfluoroalkylsulfonyl)methane represented bythe general formula [4] of the present invention is a metallic salt of aC1-C8 perfluoroalkyl sulfinic acid including, for example, atrifluoromethyl sulfinic acid, a perfluoroethyl sulfinic acid, aperfluoropropyl sulfinic acid, a perfluoroisopropyl sulfinic acid, aperfluorobutyl sulfinic acid, a perfluoroisobutyl sulfinic acid, aperfluoropentyl sulfinic acid, a perfluoroisopentyl sulfinic acid, aperfluoroneopentyl sulfinic acid and the like. An alkaline metallic saltand an alkaline earth metallic salt can be exemplified as the metallicsalt, however, the alkaline metallic salt such as sodium and the like ispreferable.

It is preferable for the nucleophilic substitution reaction of the arylhalomethane and the perfluoroalkyl sulfinate in the method for producingthe arylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] of the present invention to be conducted in a conditionwherein an arylmethylperfluoroalkylsulfone can be synthesized at a highefficiency, for example, by heating under reflux using a solvent with orwithout the presence of a catalyst. It is preferable for the molarity ofthe aryl halomethane in the reaction system mentioned above to be 0.2 to0.4 M, and for the perfluoroalkyl sulfinate such as sodiumtrifluoromethane sulfinate to be used 1.0 to 1.5 equivalent weight,especially about 1.3 equivalent weight, to the aryl halomethane. Inaddition, when a catalyst is used, the use of a catalyst comprising aniodide such as tetrabutyl ammonium iodide, potassium iodide and the likeis preferable. The amount of these catalysts to be used is, for example,2 to 20 molt, preferably 5 to 10 molt to the aryl halomethane. Further,acetonitrile, propionitrile, nitromethane, nitropropane and the like canbe given as examples of the solvent, however, it is preferable to usepropionitrile in view of the applicability of the polarity and boilingpoint.

The synthesis reaction mentioned above is preferable to be conducted byheating under reflux in a dry inert gas atmosphere, such as in an argonor nitrogen atmosphere. It is preferable for the reaction to beconducted by heating under reflux at 80 to 150° C., preferably 100° C.to 120° C for 12 to 48 hours. Examples of the methods for purifying thearylmethyl triflone obtained by these synthesis reactions are, forexample, a method wherein the reactant solution obtained by reactingunder the condition mentioned above is filtrated to remove salt,followed by a silica gel column chromatography using hexane and ethylacetate (EtOAc) as a developing solvent, and a recrystallizationoperation using hexane and toluene, or the like.

Next, the arylbis(perfluoroalkylsulfonyl)methane represented by thegeneral formula [4] can be produced by the reaction of anarylmethylperfluoroalkylsulfone produced by the nucleophilicsubstitution reaction of aryl halomethane and perfluoroalkyl sulfinatewith a deprotonation agent comprising an organic metal or a metallicsalt, followed by the reaction of the metallic salt ofarylmethylperfluoroalkylsulfone obtained with a perfluoroalkyl sulfonicacid anhydride. However, there is no particular limitation to thedeprotonation agent mentioned above, as long as it is an organic metalor a metallic salt having a deprotonating action. An alkaline metallicsalt and alkaline earth metallic salt of lower alkyl, more specifically,t-BuLi and t-BuMgCl can preferably be exemplified. Further, a preferableexample of the perfluoroalkyl sulfonic acid anhydride mentioned above isa C1-C8 perfluoroalkyl sulfonic acid anhydride including atrifluoromethane sulfonic acid anhydride (Tf₂O), a perfluoroethanesulfonic acid anhydride, a perfluoropropane sulfonic acid anhydride, aperfluoroisopropane sulfonic acid anhydride, a perfluorobutane sulfonicacid anhydride, a perfluoroisobutane sulfonic acid anhydride, aperfluoropentane sulfonic acid anhydride, a perfluoroisopentane sulfonicacid anhydride, a perfluoroneopentane sulfonic acid anhydride and thelike. Among these, Tf₂O is especially preferable.

There is no particular limitation to the method wherein thearylmethylperfluoroalkylsulfone mentioned above is reacted with adeprotonation agent such as alkyl lithium, alkyl magnesium chloride andthe like and a perfluoroalkyl sulfonic acid anhydride such as Tf₂O andthe like, as long as it is a method which can producearylbis(perfluoroalkylsulfonyl)methane such asarylbis(trifluoromethylsulfonyl)methane and the like at a high yield.Specific examples include, for example: a method wherein anarylmethylperfluoroalkylsulfone such as arylmethyl triflone and the likeis dissolved in a solvent such as a diethylether and the like, alkyllithium is added at −78° C., the solvent is reacted for 5 to 10 minutes,then Tf₂O is added after the reaction to react for 1 to 2 hours at roomtemperature; and a method wherein alkyl magnesium chloride is added at−78° C. to react for 30 minutes, then reacted at 0° C. for 30 minutes,and Tf₂O is added at −78° C. after the reaction to react for 1 to 2hours at room temperature, and the like. However, it is preferable torepeat said operation multiple times, in view of the increase in yield.

Further, in order to obtain an arylbis(perfluoroalkylsulfonyl)methanesuch as arylbis(trifluoromethylsulfonyl)methane at a high yield, it ispreferable to react 1.7 to 2.4 equivalent weight of an organic metalsuch as alkyl lithium and the like or 1.0 to 1.2 equivalent weight of aperfluoroalkyl sulfonic acid anhydride such as Tf₂O and the like withthe arylmethylperfluoroalkylsulfone such as arylmethyl triflone and thelike. For example, in the case where t-BuLi (1.2 equivalent weight) isused for a benzyl triflone, since phenylbis(triflyl)methane is a muchmore stronger acid compared to the benzyl triflone, thephenylbis(triflyl)methane produced is immediately deprotonated by thelithium salt of the benzyl triflone, the phenylbis(triflyl)methanebecomes a lithium salt, the lithium salt of thephenylbis(triflyl)methane obtained is converted to aphenyltris(triflyl)methane by the reaction with Tf₂O, the molar ratio ofthe benzyl triflone and the phenyltris(triflyl)methane becomesapproximately 1:1, and only a little amount of thephenylbis(triflyl)methane is synthesized. However, in the case where 2.2equivalent weight of t-BuLi is used for the benzyl triflone, thephenylbis(triflyl)methane produced is deprotonated by t-BuLi, and thebenzyl triflone is quantitatively converted to a lithium salt ofphenylbis(triflyl)methane.

However, in the case where a pentafluorophenylbis(triflyl)methane isproduced by using a pentafluoromethylbromide, apentafluorophenylbis(triflyl)methane and a4-tert-butyl-2,3,5,6-tetrafluorophenylbis(triflyl)methane are bothobtained at a ratio of 1:1 (45% yield, respectively). Therefore, in thiscase, using 1.0 equivalent weight of t-BuLi and 0.5 equivalent weight ofTf₂O completely suppresses the production of4-tert-butyl-2,3,5,6-tetrafluorophenylbis(triflyl)methane, and apentafluorophenylbis(triflyl)methane with Tf₂O as a base can be obtainedat a high yield.

In the metallic salt of the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [6] of the present invention[sometimes referred to as metallicarylbis(trifluoromethylsulfonyl)methide], R² shows a substituted orunsubstituted aryl group, Rf¹ and Rf² are independent to each other andshow a perfluoroalkyl group, M shows any one of the elements selectedfrom alkaline metallic element, alkaline earth metallic element,transition metallic element, silicon, germanium, tin, lead, arsenic,antimony, bismuth or tellurium, and n shows a numeric value equal to thevalence of M element. Here, examples of the metal species of metallicarylbis(trifluoromethylsulfonyl)methide include, for example: alkalinemetallic elements such as lithium, sodium, potassium, rubidium, cesiumand francium; alkaline earth metallic element such as beryllium,magnesium, calcium, strontium, barium and radium; transition metallicelements such as scandium, yttrium, lanthanum, cerium, praseodymium,neodymium, promethium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum,tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium,cobalt, rhodium, iridium, nickel, palladium, boron, aluminum, platinum,copper, silver, gold, zinc, cadmium and mercury; silicon; germanium;tin; lead; arsenic; antimony; bismuth or tellurium. Among these,lithium, scandium, silver, silicon and the like are especiallypreferable.

The R² in the formula [6] mentioned above is the same as the R²represented by the general formula [4] in the method for producing thearylbis(perfluoroalkylsulfonyl)methane of the present invention. The Rf¹and Rf² in the general formula [6] mentioned above is the same as Rf¹and Rf² in the arylbis(perfluoroalkylsulfonyl)methane represented by thegeneral formula [1] and [4] of the present invention.

Specific examples of the metallic arylbis(perfluoroalkylsulfonyl)methideof the present invention include, for example, a metallic salt ofphenylbis(triflyl)methane, a metallic salt of2-naphthylbis(triflyl)methane, a metallic salt of1-naphthylbis(triflyl)methane, a metallic salt of2,4,6-trimethylphenylbis(triflyl)methane, a metallic salt of4-(trifluoromethyl)phenylbis(triflyl)methane, a metallic salt of3,5-bis(trifluoromethyl)phenylbis(triflyl)methane, a metallic salt ofpentafluorophenylbis(triflyl)methane, a metallic salt of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane,and the like. Among these, the metallic salts such as lithium salt,scandium salt and the like are preferable, and the scandium salt andlithium salt of pentafluorophenylbis(triflyl)methane and{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane areespecially preferable in view of the catalytic activity and the like.

As to the method for producing the metallicarylbis(trifluoromethylsulfonyl)methide of the present invention, forexample, the reactions of the arylbis(trifluoromethylsulfonyl)methane ofthe present invention mentioned above can be given as follows: (1)neutralization with a hydroxide of a metal, (2) reaction by heatingunder reflux with a salt or an oxide of a transition metal, and (3)reaction with a silver carbonate under shade. Further, another methodwhich is the exchange reaction of metal species, can be exemplified,wherein a metallic salt such as a silver salt of thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4], and a halide of a metal of different metal species arereacted. Specific examples of the hydroxide of the metal in theneutralization in (1) mentioned above include the hydroxide of alkalinemetal such as lithium hydroxide, sodium hydroxide and potassiumhydroxide, and the hydroxide of alkaline earth metal such as calciumhydroxide. A method wherein said arylbis(trifluoromethylsulfonyl)methaneof the present invention is reacted for 10 minutes to over 10 hours byusing a solution wherein the hydroxides of these metals are dissolved ina solvent such as diethylether and the like, can be exemplified.Specific examples of the salt or the oxide of the transition metal inthe reaction by heating under reflux in (2) mentioned above include thelanthanoid metallic salt such as the chloride and the like of lanthanumand cerium, and scandium oxide such as Sc₂O₃ and the like. A methodwherein heating under reflux in the aqueous solution is conducted for 10minutes to over 10 hours can be exemplified.

The R² and Rf¹ and Rf² in the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general forumula [4] in the method for producing themetallic arylbis(trifluoromethylsulfonyl)methide of the presentinvention show the same group as that of R² and Rf¹ and Rf² in thegeneral formula [6] mentioned above. As a method for producing anarylbis(perfluoroalkylsulfonyl)methane, the method for producing thearylbis(trifluoromethylsulfonyl)methane in the method for producing thearylbis(trifluoromethylsulfonyl)methane of the present invention can beapplied.

There is no limitation to the catalyst such as Lewis acid catalyst andthe like comprising the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane of the present invention, as longas it is a catalyst that at least comprises a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane as an active ingredient. Forexample, a catalyst that is supported on a carrier, a catalyst that isfixed on a high polymer compound, and a catalyst having a surfaceactive-ability by making a hydrophobic atomic group and a hydrophilicatomic group exist in the molecules, can be given as specific examples.These catalysts such as Lewis acid catalyst and the like comprising themetallic salt of arylbis(perfluoroalkylsulfonyl)methane have a catalyticactivity that exceeds that of the existing Lewis acids, and therefore,they can be used for synthesis reaction of organic compounds in a highyield and with excellent selectivity.

The use of the catalyst such as Lewis acid catalyst and the likecomprising the metallic salt of thearylbis(perfluoroalkylsulfonyl)methane mentioned above makes it possibleto synthesize organic compounds such as pharmaceuticals, agriculturalchemical, asymmetric catalyst, various types of functional materials,and the like. A specific example of said method for synthesizing is amethod wherein a catalytic reaction is conducted under the presence of acatalyst such as Lewis acid catalyst or the like comprising the metallicsalt of arylbis(perfluoroalkylsulfonyl)methane mentioned above in anaqueous solution, in an organic solvent or in a mixed solvent of waterand organic solvent. Specific examples of the catalytic reactionmentioned above include a benzoylation reaction, a Diels-Alder reaction,an aldol-type reaction, a Friedel-Crafts reaction, a Mannich reaction, aglycosilation reaction, an esterification reaction, an ene reaction, acationic polymerization reaction, an allylation reaction, aninteresterification reaction, a Mannich-type reaction, a Michaeladdition reaction, an acylation reaction, a conjugate addition reaction,a dehydration reaction, a dehydration/condensation reaction, apolymerization reaction and the like.

The present invention will now be explained further in more details withthe examples below, however, the scope of the invention is not limitedto the exemplifications.

EXAMPLE 1 Analysis and Material

The infrared radiation spectrum was determined by using a ShimadzuFTIR-9100. The ¹H NMR spectrum was determined by using a VarianGemini-300 (300 MHz) nuclear magnetic resonance apparatus. The chemicalshift of ¹H NMR was indicated by ppm wherein a solvent as an internalstandard (tetramethylsilane at 0 ppm) was used. The division pattern wasshown as singlet: s, doublet: d, triplet: t, quartet: q, multiplet: mand broad peak: br. The ¹³C NMR spectrum was determined by using aVarian Gemini-300 (125 MHz) nuclear magnetic resonance apparatus, andwas indicated by ppm wherein a solvent as an internal standard (CDCl₃at77.0 ppm) was used. The ¹⁹F NMR spectrum was determined by using aVarian Gemini-300 (282 MHz) nuclear magnetic resonance apparatus, andwas indicated by ppm wherein a solvent as an internal standard (CF₃C₆H₅at −64.0 ppm) was used. High-performance liquid chromatography (HPLC)analysis was conducted with a Shimadzu LC-10AD instrument and anSPD-M10A UV detector by using a chiral column (Daicel, AS or OD-H). Allof the following examples were conducted in a glass instrument dried inan oven, by using a magnetic stirrer. The reaction product was purifiedon a Silica Gel E. Merck 9385 or a Silica Gel 60 Extra Pure by flashchromatography. High resolution mass spectrometry (HRMS) analysis wasperformed with the use of an instrument of Daikin Industries, Ltd.

EXAMPLE 2 Synthesis of Arylmethyl Triflone

Each of the mixed solutions of aryl halomethyl (10 mmol), sodiumtrifluoromethane sulfinate (2.0 g: 13 mmol), propionitrile (30 mL) andtetrabutyl ammonium iodide (0.37 g: 1 mmol), shown in Table 1, weresubjected to heating under reflux in an argon atmosphere forapproximately 1 day. After the heating under reflux, the reactionsolutions were cooled to room temperature, and were concentrated afterremoving the salt by filtration. The crude products obtained werepurified by silica gel column chromatography (developing solvent:hexane-EtOAc) or recrystallization operation (hexane-toluene) to obtainarylmethyl triflone. The yield of each of the arylmethyl triflone isindicated in Table 1, and the physical property of each of thearylmethyl triflone is shown below. Table 1 showed that when sodiumtrifluoromethane sulfinate (TfNa) used as an electrophilic reactant as atriflyl source, and heating under reflux with aryl halomethane wasconducted by using propionitrile as a solvent under the presence of atetrabutyl ammonium iodide catalyst, arylmethyl triflone can be obtainedat a high yield than the method of Hendrickson et al. (Synthesis, 691,1997). TABLE 1 aryl halomethane arylmethyl triflone [yield (%)] PhCH₂BrPhCH₂Tf 94 2-NaphCH₂Br 2-NaphCH₂Tf >99 1-NaphCH₂Cl 1-NaphCH₂Tf 992,4,6-Me₃C₆H₂CH₂Cl 2,4,6-Me₃C₆H₂CH₂Tf 90 4-CF₃C₆H₄CH₂Br4-CF₃C₆H₄CH₂Tf >99 3,5-(CF₃)₂C₆H₃CH₂Br 3,5-(CF₃)₂C₆H₃CH₂Tf 76 C₆F₅CH₂BrC₆F₅CH₂Tf 89

Benzyl triflone (2-Benzyl Triflone; J. Fluorine Chem. 66, 301, 1994): IR(KBr) 1362, 1347, 1223, 1198, 1188, 1125, 776, 698, 640, 525, 507 cm⁻¹;¹H NMR (CDCl₃, 300 MHz) δ 4.48 (s, 2H), 7.42-7.47 (m, 5H); ¹⁹F NMR(CDCl₃, 282 MHz) δ −77.6 (s, 3F, CF₃).

2-naphthylmethyl triflone (2-Naphthylmethyl Triflone): IR (KBr) 1358,1345, 1221, 1194, 1125, 831, 756, 658, 608, 486 cm⁻¹; ¹H NMR (CDCl₃, 300MHz) δ 4.65 (s, 2H), 7.50 (dd, J=1.8, 8.4 Hz, 1H), 7.54-7.58 (m, 2H),7.86-7.94 (m, 4H); ¹³C NMR (CDCl₃, 125 MHz) 656.3, 119.8 (q, J_(CF)=326Hz, 1C), 120.3, 126.9, 127.4, 127.5, 127.8, 128.1, 129.2, 131.5, 133.1,133.6; ¹⁹F NMR (CDCl₃, 282 MHz) δ −77.6 (s, 3F, CF₃). Anal. Calcd. forC₁₂H₉O₂F₃S: C, 52.55; H, 3.31; F, 20.78; S, 11.69. Found C, 52.51; H,3.33; F, 20.81; S, 11.65.

1-naphthylmethyl triflone (1-Naphthylmethyl Triflone): IR (KBr) 1510,1358, 1223, 1200, 804, 776, 658, 486 cm⁻¹; ¹H NMR (CDCl₃, 300 MHz) δ4.99 (s, 2H), 7.53 (dd, J=7.8, 8.4 Hz, 1H), 7.62 (d, J=7.8 Hz, 1H), 7.58(ddd, J=0.9, 6.9, 8.3 Hz, 1H), 7.65 (ddd, J=1.5, 6.9, 8.4 Hz, 1H), 7.93(dd, J=1.5, 8.3 Hz, 1H), 7.98 (dd, J=8.4 Hz, 1H), 8.04 (dd, J=0.9, 8.4Hz, 1H); ¹³C NMR (CDCl₃, 125 MHz) δ 53.0, 119.2, 120.0 (q. J_(CP)=326Hz, 1C), 123.3, 125.3, 126.5, 127.5, 129.0, 131.1, 131.5, 132.3, 134.0;¹⁹F NMR (CDCl₃, 282 MHz) δ −78.1 (s, 3F, CF₃). Anal. Calcd. forC₁₂H₉O₂F₃S: C, 52.55; H, 3.31; F, 20.78; S, 11.69. Found C, 52.53; H,3.29; F, 20.75; S, 11.73.

2,4,6-trimethylphenylmethyl triflone (2,4,6-TrimethylphenylmethylTriflone): IR (KBr) 1358, 1206, 1117, 864, 619, 550, 500, 469 cm⁻¹; ¹HNMR (CDCl₃, 300 MHz) δ 2.29 (s, 3H), 2.43 (s, 6H) 4.62 (s, 2H), 6.96 (s,2H); ¹³C NMR (CDCl₃, 125 MHz) δ 20.3, 21.0 (2C), 49.8, 117.0, 120.0 (q,J_(CF)=326 Hz, 1C, CF₃), 129.9 (2C), 139.7 (2C), 139.8; ¹⁹F NMR (CDCl₃,282 MHz) δ −79.7 (s, 3F, CF₃). Anal. Calcd. for C₁₁,H₁₃O₂F₃S: C, 49.62;H, 4.92; F, 21.40; S, 12.04. Found C, 49.58; H, 4.53; F, 21.35; S,12.06.

4-(trifluoromethyl)phenylmethyl triflone(4-(Trifluoromethyl)phenylmethyl Triflone; Synthesis, 691, 1997): IR(KBr) 1356, 1341, 1227, 1210, 1144, 1121, 855, 658, 513 cm⁻¹; ¹H NMR(CDCl₃, 300 MHz) 64.53 (s, 2H), 7.58 (d, J=8.0 Hz, 2H), 7.72 (d, J=8.0Hz, 2H); ¹⁹F NMR (CDCl₃, 282 MHz) δ −77.5 (s, 3F, CF₃), −64.3 (s, 3F,CF₃).

3,5-bis(trifluoromethyl)phenylmethyl triflone(3,5-Bis(trifluoromethyl)phenylmethyl Triflone): IR (KBr) 1376, 1362,1277, 1175, 1117, 918, 910, 669 cm⁻¹; ¹H NMR (CDCl₃, 300 MHz) δ 4.60 (s,2H), 7.91 (s, 2H), 8.01 (s, 1H); ¹³C NMR (CDCl₃, 125 MHz) δ 55.0, 119.6(q, J_(CF)=326 Hz, 1C, CF₃), 122.6 (q, J_(CF)=272 Hz, 2C, 2CF₃), 124.2(septet, J_(CP)=4 Hz, 1C), 126.1, 131.3 (2C), 132.9 (q, J_(CP)=34 Hz,2C); ¹⁹F NMR (CDCl₃, 282 MHz) δ −77.4 (s, 3F, CF₃), −64.3 (s, 6F, 2CF₃).Anal. Calcd. for C₁₀H₃O₂F₉S: C, 33.53; H, 0.84; F, 47.74; S, 8.95. FoundC, 33.48; H, 0.91; F, 47.87; S, 8.89.

Pentafluorophenylmethyl triflone (Pentafluorophenylmethyl Triflone): IR(KBr) 1509, 1374, 1210, 1121, 995 cm⁻¹; ¹H NMR (CDCl₃, 300 MHz) δ 4.64;¹³C NMR (CDCl₃, 125 MHz) δ 44.3, 100.0 (dt, J_(CF)=4, 17 Hz, 1C,ipso-C), 119.5 (q, J_(CF)=326 Hz, 1C, CF₃), 137.9 (d, J_(CF)=251 Hz, 2C,2m-C), 142.8 (d, J_(CP)=258 Hz, 1C, p-C), 145.9 (d, J_(CF)=252 Hz, 2C,2o-C); ¹⁹F NMR (CDCl₃, 282 MHz) δ −160.0 (d, J=15.2Hz, 2F, 2m-F), 149.0(s, 1F, p-F), 139.4 (d, J=15.2 Hz, 2F, 2o-F), −78.3 (s, 3F, CF₃). Anal.Calcd. for C₈H₂O₂F₈S: C, 30.59; H, 0.64; F. 48.38; S, 10.21. Found C,30.49; H, 0.73; F, 48.37; S, 10.18.

EXAMPLE 3 Examination of the Method for SynthesizingArylbis(triflyl)methane

The benzyl triflone obtained from Example 2 (0.5 mmol) was dissolved indiethylether (3 mL), this solution was cooled to −78° C., then addedwith 2.2 equivalent weight (1.1 mmol) of t-BuLi (0.34 mL, 1.6 M pentanesolution), and was stirred for 0.5 hour. Next, after Tf₂O (46 μL, 0.55mmol) was added, the temperature of the reaction solution was raised toroom temperature, and the solution was further stirred for 1 hour.Subsequently, water was added to stop the reaction, the solution wasneutralized, and then washed with hexane. These aqueous phases wereacidified with 4 M of hydrochloride, and were twice extracted withdiethylether. The organic phase was dried, filtrated and concentratedwith magnesium sulfate to obtain phenylbis(triflyl)methane [PhCHTf₂] asa solid (79% yield). However, only a small amount ofphenyltris(triflyl)methane [PhCTf₃] was produced. Meanwhile, the samereaction as mentioned above, except for the use of 1.1 equivalent weightof t-BuLi instead of 2.2 equivalent weight of t-BuLi, was conducted, andthe yield of PhCHTf₂ was 6% and that of PhCTf₃ was 46%.

EXAMPLE 4 Synthesis of Arylbis(triflyl)methane

Each of the arylmethyl triflone (0.5 mmol) obtained from Example 2 weredissolved in diethylether (3 mL), and their solutions were prepared,respectively. These solutions were cooled to −78° C., then added with1.1 equivalent weight (0.55 mmol) of t-BuLi (0.34 mL, 1.6 M pentanesolution), and were stirred for 10 minutes. Next, Tf₂O (46 μL, 0.275mmol) was added, the temperature of the reaction solution was raised toroom temperature, and the solution was further stirred for 1 hour. Aftercooling the solution again to −78° C., 1.1 equivalent weight (0.55 mmol)of t-BuLi (0.34 mL, 1.6 M pentane solution) was added, and the solutionwas stirred for 10 minutes. Subsequently, Tf₂O (46 μL, 0.275 mmol) wasadded, the temperature of the reaction solution was raised to roomtemperature, and the solution was further stirred for 1 hour. Then,water was added to stop the reaction, the solution was neutralized, andthen washed with hexane. These aqueous phases were acidified with 4 M ofhydrochloride, and were twice extracted with diethylether. The organicphase was dried, filtrated and concentrated with magnesium sulfate toobtain arylbis(triflyl)methane as a solid. No further purification wasneeded. The yield of each of the arylmethyl triflone is indicated inTable 2, and the physical property of each of the arylmethyl triflone isshown below. TABLE 2 arylmethyl triflone arylbis(triflyl)methane [yield(%)] 2-NaphCH₂Tf 2-NaphCHTf₂ 84 1-NaphCH₂Tf 1-NaphCHTf₂ 982,4,6-Me₃C₆H₂CH₂Tf 2,4,6-Me₃C₆H₂CHTf₂ 89 4-CF₃C₆H₄CH₂Tf 4-CF₃C₆H₄CHTf₂87 3,5-(CF₃)₂C₆H₃CH₂Tf 3,5-(CF₃)₂C₆H₃CHTf₂ 75 C₆F₅CH₂Tf C₆F₅CHTf₂ 45

Phenylbis(triflyl)methane (Phenylbis(triflyl)methane; J. Org. Chem. 38,3358, 1973; Heteroatom Chem. 5, 9, 1.994): IR (KBr) 2950, 1381, 1242,1219, 1184, 1102, 806, 695, 660, 608, 585; 507 cm⁻¹; ¹H NMR (CDCl₃, 300MHz) δ 5.97 (s, 1H), 7.54-7.68 (m, 5H); ¹³C NMR (CDCl₃, 125 MHz) δ 80.7,119.3, 119.3 (q, J_(CF)=329 Hz, 2C, 2CF₃), 130.0 (2C), 131.8 (br), 132.9(2C); ¹⁹F NMR (CDCl₃, 282 MHz) −73.8 (s, 6F, 2CF₃).

2-naphthylbis(triflyl)methane (2-Naphthylbis(triflyl)methane): IR (KBr)1393, 1381, 1244, 1213, 1103, 646, 586 cm⁻¹; ¹H NMR (CDCl₃, 300 MHz) δ6.10 (s, 1H), 7.61-7.71 (m, 3H), 7.92-7.99 (m, 2H), 8.03 (d, J=8.4 Hz,2H); ¹³C NMR (CDCl₃, 75 MHz) δ 80.9, 116.3, 119.3 (q, J_(CF)=329 Hz, 2C,2CF₃), 127.7, 128.0, 128.8, 129.1, 130.1, 132.8, 133.4, 134.7; ¹⁹F NMR(CDCl₃, 282 MHz) δ −73.6 (s, 6F. 2CF₃); HRMS (EI) calcd for C₁₃H₆O₄F₆S₂[M]⁺ 405.9768, found 405.9761.

1-naphthylbis(triflyl)methane (1-Naphthylbis(triflyl)methane): IR (KBr)1389, 1383, 1215, 1111, 770, 650, 504 cm⁻¹; ¹H NMR (CDCl₃, 300 MHz) δ6.87 (s, 1H), 7.62-7.80 (m, 4H), 8.02 (d, J=8.4 Hz, 1H), 8.16 (d, J=8.4Hz, 1H), 8.37 (d, J=7.5 Hz, 1H); ¹³C NMR (CDCl₃, 75 MHz) δ 74.6, 114.1(s, 1C, ipso-C), 119.4 (q, J_(CF)=328 Hz, 2C, 2CF₃), 119.9, 125.4,127.0, 128.9, 130.1, 131.5, 131.7. 133.8, 134.0; ¹⁹F NMR (CDCl₃, 282MHz) δ −74.2 (s, 6F, 2CF₃); HRMS (EI) calcd for C₁₃H₈O₄F₆S₂ [M]⁺405.9768, found 405.9761.

2,4,6-trimethylphenylbis(triflyl)methane(2,4,6-Trimethylphenylbis(triflyl)methane): IR (KBr) 1397, 1383, 1217,1119, 1107, 642, 590 cm⁻¹; ¹H NMR (CDCl₃, 300 MHz) δ 2.33 (s, 3H), 2.35(s, 3H), 2.61 (s, 3H), 6.48 (s, 1H), 7.00 (s, 1H), 7.08 (2, 1H); ¹³C NMR(CDCl₃, 75 MHz) δ 20.2, 21.1, 22.2, 77.7, 115.9, 119.4 (q, J_(CF)=328Hz, 2C, 2CF₃), 130.4, 132.2, 140.0, 142.2, 142.6; ¹⁹F NMR (CDCl₃, 282MHz) δ −76.3 (s, 6F, 2CF₃); HRMS (EI) calcd for C₁₂H₁₂O₄F₆S₂ [M]⁺398.0081, found 398.0089.

4-(trifluoromethyl)phenylbis(triflyl)methane(4-(Trifluoromethyl)phenylbis(triflyl)methane): IR (KBr) 1393, 1383,1327, 1231, 1171, 1136, 1111, 860, 671, 610 cm⁻¹; ¹H NMR (CDCl₃, 300MHz) 65.98 (s, 1H), 7.84 (s, 4H); ¹³C NMR (CDCl₃, 125 MHz) δ 80.4, 120.0(q, J_(CF)=329 Hz, 2C, 2CF₃), 123.8 (q, J_(CP)=271 Hz, 1C, CF₃), 124.2,127.6 (q, J=4 Hz, 2C), 133.0 (2C), 135.6 (q, J_(CF)=33 Hz, 1C); ¹⁹F NMR(CDCl₃, 282 MHz) δ −73.5 (s, 6F, 2CF₃), −64.7 (s, 3F, CF₃); HRMS (EI)calcd. for C₁₀H₅O₄F₉S₂ [M]⁺ 423.9486, found 423.9471.

3,5-bis(trifluoromethyl)phenylbis(triflyl)methane(3,5-Bis(trifluoromethyl)phenylbis(triflyl)methane): IR (KBr) 1395,1374, 1285, 1223, 1194, 1179, 1144, 1105, 936, 909, 629, 519 cm⁻¹; ¹HNMR (CDCl₃, 300 MHz) δ 6.05 (s, 1H), 8.13 (s, 2H), 8.18 (s, 1H); ¹³C NMR(CDCl₃, 125 MHz) 678.9, 119.2 (q, J_(CP)=329 Hz, 2C, 2CF₃), 122.2 (q,J_(CF)=272 Hz, 2C, 2CF₃), 122.9, 126.7 (septet, J_(CF)=4 Hz), 131.6 (s,2C), 133.8 (q, J=35 Hz, 2C); ¹⁹F NMR (CDCl₃, 282 MHz) δ −73.2 (s, 6F,2CF₃), −64.3 (s, 6F, 2CF₃); HRMS (EI) calcd for C₁₁H₄O₄F₁₂S₂ [M]⁺472.9375, found 472.9372.

Pentafluorophenylbis(triflyl)methane(Pentafluorophenylbis(triflyl)methane): Mp. 86° C. to 87° C.; IR (KBr)1522, 1501, 1347, 1321, 1198, 1127, 1024, 988, 613 cm⁻¹; ¹H NMR (CDCl₃,300 MHz) δ 6.21 (brs, 1H); ¹³C NMR (CDCl₃, 125 MHz) δ 70.4, 98.0 (s, 1C,ipso-C), 119.2 (q, J_(CF)=330 Hz, 2C, 2CF₃), 137.8 (d, J_(CF)=258 Hz,1C, m-C), 138.6 (d, J_(CP)=257 Hz, 1C, m-C), 144.7 (d, J_(CF)=264 Hz,1C, p-C), 145.4 (d, J_(CF)=262 Hz, 1C o-C), 147.2 (d, J_(CF)=262 Hz, 1C,o-C); ¹³C NMR (CD₃OD (δ49.0), 125 MHz) 656.2, 109.1 (dt, J=6, 19 Hz, 1C,ipso-C), 122.4 (q, J_(CP)=324 Hz, 2C, 2CF₃) 138.5 (d, J_(CF)=250 Hz, 2C,2m-C), 143.0 (d, J_(CP)=251 Hz, 1C, p-C), 150.0 (d, J_(CF)=245 Hz, 1C,o-C), ¹⁹F NMR (CDCl₃, 282 MHz) δ −157.9 (dt, J=6.2, 21.5 Hz, 1F, m-F),−156.8 (dt, J=6.2, 21.5 Hz, 1F, m-F), −142.6 (tt, J=5.9, 21.5 Hz, 1F,p-F), −140.3 (br, 1F, o-F), −127.7 (ddd, J=5.9, 15.2, 21.5 Hz, 1F, o-F),−75.2 (s, 6F, 2CF₃); HRMS (EI) calcd. for C₉HO₄F₁₁S₂ [M]⁺ 445.9141,found 445.9137.

EXAMPLE 5 Nucleophilic Substitution Specific to the Para Position ofPentafluorophenylbis(triflyl)methane

As it is described in Table 2 that the yield ofpentafluorophenylbis(triflyl)methane is 45%, it was revealed that whenpentafluorophenylbis(triflyl)methane is produced using apentafluoromethylbromide, both of pentafluorophenylbis(triflyl)methaneand 4-tert-butyl-2,3,5,6-tetrafluorophenylbis(triflyl)methane can beobtained at a ratio of 1:1 (45% yield, respectively). However, it wasfound out that when 1.0 equivalent weight of t-BuLi and 0.5 equivalentweight of Tf₂O are used, the production of4-tert-butyl-2,3,5,6-tetrafluorophenylbis(triflyl)methane is completelysuppressed, and pentafluorophenylbis(triflyl)methane can be obtained at95% yield with Tf₂O as a base. Consequently, the reactions ofpentafluorophenylbis(triflyl)methane with the various types of alkyllithium reagents were examined, in order to determine the generality andrange of the nucleophilic substitution specific to the para position ofpentafluorophenylbis(triflyl)methane. Table 3 shows the types of alkyllithium reagents, the reaction conditions and the yield of the paraposition substituents of pentafluorophenylbis(triflyl)methane. The paraposition substituents of pentafluorophenylbis(triflyl)methane shown inTable 3 are obtained by washing the reaction product obtained byreacting pentafluorophenylbis(triflyl)methane with alkyl lithiumreagent, with a hydrochloric solution. The “Bn” shown in Table 3represents a benzyl group. TABLE 3

RLi (equivalent weight) Condition 5, yield (%) t-BuLi (3) −78° C., 1 h87 BuLi (3) −78° C., 1 h >95 BnLi (5) −78° C., 6 h 83 PhLi (3) −78° C.to rt, 1 day >95 3,4,5-F₃C₆H₂Li (5) −20° C. to rt, 3 h 753,5-(CF₃)₂C₆H₃Li (5) −20° C. to rt, 3 h 70

EXAMPLE 6 Synthesis of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl)bis(triflyl)methane

Synthesis of 4-methylperfluorobiphenyl;

A diethylether solution of methyl lithium (13 mL, 15 mmol) was droppedfor 0.5 hour to a THF (50 mL) solution dissolved with perfluorobiphenyl(10 g, 30 mmol), at −78° C. under argon atmosphere. Then, after thesolution was stirred at the same temperature for 2 hours, it was furtherstirred at room temperature for 2 hours. Water was added to stop thereaction, diethylether was used for extraction, and its organic phasewas dried with magnesium sulfate. After filtration was conducted, thesolvent was removed under reduced pressure, and a mixture of4-methylperfluorobiphenyl, 4,4′-dimethylperfluorobiphenyl andperfluorobiphenyl (molar ratio, 30:3:67) was obtained as a crudeproduct.

Synthesis of 4-(bromomethyl)perfluorobiphenyl;

A mixed solution of a mixture comprising the 4-methylperfluorobiphenylmentioned above, an N-bromo succinic imide (NBS) (26.7 g, 150 mmol),AIBN (0.99 g, 6 mmol) and a carbon tetrachloride (100 mL) was subjectedto heating under reflux for 1 week. During this process, the progress ofthe reaction was confirmed by TLC, and NBS and AIBN were added on atimely basis. Ultimately, 285 mmol NBS and 15 mmol AIBN were added tothe solution. After the reaction was completed, the solution was cooledto room temperature, and the solvent was removed under reduced pressure.The crude product was purified by silica gel column chromatography(developing solvent: hexane-ethyl acetate=100:1), and the4-(bromomethyl)perfluorobiphenyl (7.36 g, 18 mmol, total yield frommethyl lithium 60%) was isolated.

¹H NMR (CDCl₃, 300 MHz) δ 4.58 (s, 2H, CH₂Br); ¹⁹F NMR (CDCl₃, 282 MHz)δ −138.02 (dd, J=10.6, 19.8 Hz, 2F), −138.56 (dt, J=9.1, 20.3 Hz, 2F),−142.36 (dd, J=10.6, 19.8 Hz, 2F), −150.59 (t, J=20.3 Hz, 1F), −161.08(dt, J=7.1, 20.3 Hz, 2F).

Synthesis of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}(triflyl)methane;

4-bromomethylperfluorobiphenyl (3.68 g, 9 mmol) and sodiumtrifluoromethane sulfinate (1.69 g, 10.8 mmol) were dissolved inpropionitrile (30 mL), and the resultant solution was subjected toheating under reflux for 12 hours. After the reaction, the solution wascooled to room temperature, and water was added for extraction withethyl acetate. The organic phase was dried with magnesium sulfate,filtrated, and the solvent was removed under reduced pressure. The crudeproduct was purified by silica gel column chromatography (hexane-ethylacetate=20:1 to 8:1 to 1:1), and the aimed{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}(triflyl)methane (3.91g, 8.46 mmol, 94% yield) was isolated.

¹H NMR (CDCl₃, 300 MHz) δ 4.75 (s, 2H, CH₂Tf); ¹⁹F NMR (CDCl₃, 282 MHz)δ −78.24 (s, 3F, CF₃), −136.82 to −136.62 (m, 1F), −137.72 (dd, J=10.7,18.3 Hz, 2F), −138.84 (dd, J=10.7, 18.3 Hz, 2F), −149.69 (t, J=21.3 Hz,1F), −160.63 (dt, J=6.1, 21.3 Hz, 2F).

Synthesis of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane;

A tert-butyl magnesium chloride (5 mL, 10 mmol, 2.0 M diethylethersolution) was added to a diethylether (120 mL) solution dissolved with{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}(triflyl)methane (4.6g, 10 mmol), at −78° C. under argon atmosphere. After the reactionsolution was stirred for 0.5 hour at −78° C., it was further stirred for0.5 hour at 0° C. Then, the solution was cooled again to −78° C.,trifluoromethane sulfonic acid anhydride (0.84 mL, 5 mmol) was added,and the resultant solution was stirred for 2 hours at room temperature.Further, tert-butyl magnesium chloride (3.75 mL, 7.5 mmol, 2.0 Mdiethylether solution) was added at −78° C. After the reaction solutionwas stirred at −78° C. for 0.5 hour, it was stirred at 0° C. for 0.5hour. The solution was cooled again to −78° C., trifluoromethanesulfonicacid anhydride (0.84 mL, 5 mmol) was added, and the resultant solutionwas stirred for 2 hours at room temperature. After the reaction wascompleted, water was added, further neutralized with 1 M hydrochloricacid water, and the water phase was washed with hexane. Then, said waterphase was acidified with 4 M hydrochloric acid water, and extracted withdiethylether. The organic phase was dried with magnesium sulfate,filtrated, and the solvent was removed under reduced pressure. The crudeproduct was sublimated (8 to 9 Pa, 150° C., and the aimed{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane(2.79 g, 4.7 mmol, 47% yield) was isolated.

¹H NMR (CDCl₃, 300 MHz) δ 6.32 (s, 1H, CH), ¹⁹F NMR (CDCl₃, 282 MHz) δ−75.1 (s, 6F, 2CF₃), −127.72 to −127.58 (m, 1F), −133.43 (dt, J=10.2,21.3 Hz, 1F), −134.60 (dt, J=9.4, 21.3 Hz, 1F), −137.08 to −137.35 (m,2F), −140.07 (br, 1F), −148.38 (t, J=21.3 Hz, 1F), −160.01 (dt, J=6.2,21.3 Hz, 2F).

EXAMPLE 7 Synthesis of 4′ Position Alkyl Substituent of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane

Phenyl lithium (0.28 mL, 0.3 mmol, 1.06 M cyclohexane-diethylether mixedsolution) was added to a diethylether (1 mL) solution dissolved with{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane (59mg,0.1 mmol), at −78° C. under argon atmosphere. The temperature of thereaction solution was slowly raised to −40° C., and the solution wasstirred for 1 hour. Water was added to stop the reaction, the solutionwas neutralized with 1 M hydrochloric acid water, and the water phasewas washed with hexane. Subsequently, the solution was acidified with 4M hydrochloric acid water, and extracted with diethylether. The organicphase was dried with magnesium sulfate, filtrated, and the solvent wasremoved under reduced pressure. The product obtained thereby was theaimed compound,{4-(4-phenyl-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane(57.2 mg, 0.088 mmol, 88% yield), and no further purification wasrequired.

¹H NMR (CDCl₃, 300 MHz) δ 6.33 (s, 1H, CH), 7.54 (s, 5H, C₆H₅); ¹⁹F NMR(CDCl₃, 282 MHz) δ −75.15 (s, 6F, 2CF₃), −128.03 (dt, J=10.5, 21.2Hz,1F), −133.35 (dt, J=10.5, 21.2 Hz, 1F), −134.52 (dt, J=10.5, 21,2 Hz,1F), −138.73 to −138.53 (m, 2F), −140.42 (br, 1F), −142.66 to −142.53(m, 2F).

EXAMPLE 8 Synthesis of 4′ Position Alkoxy Substituent of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane

Hexanol (1.5 mL, 12 mmol) was added to a pyridine (10 mL) solutiondissolved with 60% sodium hydride containing mineral oil (0.56 g, 14mmol) at 0° C., and the resultant solution was stirred for 1 hour atroom temperature. After the solution was cooled to −20° C.,(4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane(1.2 g, 2 mmol) was added. The reaction solution was stirred at −20° C.for 5 hours. After the reaction, the solution was acidified with 4 Mhydrochloric acid water, and was extracted with diethylether. Afterdrying with magnesium sulfate, the solution was filtrated, and thesolvent was removed under reduced pressure. The crude product waspurified by sublimation (0.2 to 0.3 torr, 80° C.), and{4-(4-hexanoxy-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methanewas obtained at 94% yield (1.27 g, 1.88 mmol).

¹H NMR (CDCl₃, 300 MHz) δ 0.83 to 0.94 (m, 3H), 1.26 (br, 2H), 1.33 to1.38 (m, 2H), 1.45 to 1.52 (m, 2H), 1.84 (5, J=6.8 Hz, 2H), 4.38 (t,J=6.8 Hz, 2H), 4.32 (s, 1H); ¹⁹F NMR (CDCl₃, 282 MHz) δ −75.0 (s, 6F,2CF₃), −128.4 to −128.3 (m, 1F), −133.6 (dt, J=9.1, 21.3 Hz, 1F), −134.8(dt, J=9.1, 21.3 Hz, 1F), −139.8 to −139.6 (m, 2F), −140.7 (br, 1F),−156.5 (d, J=19.7 Hz, 2F).

EXAMPLE 9 Synthesis of Para Position Alkoxy Substituent ofPentafluorophenylbis(triflyl)methane

Hexanol (1.5 mL, 12 mmol) was added to a pyridine (10 mL) solutiondissolved with 60% sodium hydride containing mineral oil (0.56 g, 14mmol) at 0° C., and the resultant solution was stirred for 1 hour atroom temperature. After the solution was cooled to −20° C.,pentafluorophenylbis(triflyl)methane (0.89 g, 2 mmol) was added. Thereaction solution was stirred at −20° C. for 5 hours. After thereaction, the solution was acidified with 4 M hydrochloric acid water,and was extracted with diethylether. After drying with magnesiumsulfate, the solution was filtrated, and the solvent was removed underreduced pressure. The crude product was purified by sublimation (0.2 to0.3 torr, 65° C.), and 4-hexanoxy-2,3,5,6-tetrafluorophenylbis(triflyl)methane was obtained at 99% yield (1.02g, 1.98 mmol).

¹H NMR (CDCl₃, 300 MHz) δ 0.91 (t, J=7.1 Hz, 3H), 1.32 to 1.37 (m, 4H),1.43 to 1.51 (m, 2H), 1.83 (quintet, J=6.8 Hz, 2H), 4.44 (t, J=6.8 Hz,2H), 6.19 (s, 1H); ¹⁹F NMR (CDCl₃, 282 MHz) δ −75.35 (s, 6F, 2CF₃),−130.64 (dt, J=9.9, 21.2 Hz, 1F), −143.16 (br, 1F), −155.31 (d, J=21.2Hz, 1F).

EXAMPLE 10 Synthesis of Lithium Pentafluorophenylbis(triflyl)methide

The pentafluorophenylbis(triflyl)methane obtained from Example 4 (1mmol) and LiOH.H₂O (1 mmol) were dissolved in a diethylether (10 mL),the resultant solution was stirred at room temperature for 12 hours,then concentrated and dried to obtain a white powder, lithiumpentafluorophenylbis(triflyl)methide (100% yield). The physical propertyof this lithium pentafluorophenylbis(triflyl)methide obtained is asfollows.

Lithium pentafluorophenylbis(triflyl)methide (LithiumPentafluorophenylbis(triflyl)methide): ¹³C NMR (CD₃OD, 125 MHz) δ 56.1,109.0 (dt, J=4, 19 Hz, 1C, ipso-C), 122.3 (q, J_(CF)=324 Hz, 2C, 2CF,),138.5 (d, J_(CP)=247 Hz, 2C, 2m-C), 143.0 (d, J_(CF)=251 Hz, 1C, p-C),149.5 (d, J_(CF)=245 Hz, 2C, 2o-C).

EXAMPLE 11 Synthesis ofLithium{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methide

The {4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methaneobtained from Example 6 (1 mmol) and LiOH.H₂O (1 mmol) were dissolved ina diethylether (10 mL), the resultant solution was stirred at roomtemperature for 12 hours, then concentrated and dried to obtain a whitesolid,lithium{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methide(100% yield).

EXAMPLE 12 Synthesis of Silver (I) Pentafluorophenylbis(triflyl)methide

Ag₂CO₃ (66 mg, 0.24 mmol) was added to an aqueous solution (3 mL) ofpentafluorophenylbis(triflyl)methane (0.20 g, 0.40 mmol) in a reactionflask wherein light was shut out by an aluminum foil. The solution wasstirred at room temperature for 12 hours, then filtrated if there wereany solid remaining, followed by concentration. A white solid of silver(I) pentafluorophenylbis(triflyl)methide was obtained thereby (99% yieldor more). The physical property of this silver (I)pentafluorophenylbis(triflyl)methide obtained is as follows.

Silver (I) pentafluorophenylbis(triflyl)methide (Silver(I)Pentafluorophenylbis(triflyl)methide): ¹⁹F NMR (CDCl₃, 282 MHz) δ −162.6(dt, J=7.6, 21.4 Hz, 2F, 2m-F), −150.6 (t, J=21.4 Hz, 1F, p-F),−134.7-134.6 (m, 2F, 20-F), −79.5 (s, 6F, 2CF₃).

EXAMPLE 13 Synthesis of Scandium (III)Pentafluorophenylbis(triflyl)methide (Part 1)

Sc₂O₃ (21 mg, 0.155 mmol) and pentafluorophenylbis(triflyl)methane(0.277 g, 0.62 mmol) were subjected to heating under reflux in water(0.5 mL) for 12 hours. Then, the unreacted Sc₂O₃ was removed byfiltration and condensation was conducted. The crude product obtainedwas washed with chloroform, the unreactedpentafluorophenylbis(triflyl)methane was removed, pressure was reducedby a vacuum pump, and then dried at 100° C. to obtain a white powder ofscandium (III) pentafluorophenylbis(triflyl)methide (50% yield).

EXAMPLE 14 Synthesis of Scandium (III)Pentafluorophenylbis(triflyl)methide (Part 2)

The silver (I) pentafluorophenylbis(triflyl)methide obtained fromExample 12 (0.19 g, 0.34 mmol) and Sc (III) Cl₃.(H₂O)₆ (29 mg, 0.11mmol) were stirred in a diethylether (3 mL) at room temperature for 12hours. Then, silver chloride was removed by filtration and condensationwas conducted. The unreacted pentafluorophenylbis(triflyl)methane wasremoved, pressure was reduced by a vacuum pump, and then dried at 100°C. to obtain a white powder of scandium (III)pentafluorophenylbis(triflyl)methide (50% yield). The physical propertyof the scandium (III) pentafluorophenylbis(triflyl)methide obtained fromthe present Example and Example 13 is as follows.

Scandium (III) pentafluorophenylbis(triflyl)methide (Scandium(III)Pentafluorophenylbis(triflyl)methide): Mp.>250° C. (decomposed); ¹³C NMR(CD₃OD (δ 49.0), 125 MHz) δ 56.2, 109.0 (dt, J_(CF)=2, 20 Hz, 1C,ipso-C), 122.3 (q, J_(CP)=324 Hz, 2C, 2CF₃), 137.8 (d, J_(CP)=247 Hz,2C, 2m-C), 142.3 (d, J_(CP)=251 Hz, 1C, p-C), 148.9 (d, J_(CF)=245 Hz,2C, 20-C); ¹⁹F NMR (CD₃OD, 282 MHz) δ −166.4 (dt, J=6.1, 21.3 Hz, 2F,2m-F), −155.9 (t, J=21.3 Hz, 1F, p-F), −134.9 to −134.9 (m, 2F, 20-F),−80.9 (s, 6F, 2CF₃).

EXAMPLE 15 Benzoylation Reaction of Menthol

Benzoylation reaction was conducted to a menthol wherein the scandium(III) pentafluorophenylbis(triflyl)methide obtained from Examples 13 and14 was used as a Lewis acid catalyst (Chemical formula 38). 1-menthol(0.18 g, 1 mmol) and benzoic anhydride (0.34 g, 1.5 mmol) were reactedwhile stirring in acetonitrile (4.8 mL) at 26° C. for 1 day, under thepresence of the scandium (III) pentafluorophenylbis(triflyl)methide as 1mol % of Lewis acid catalyst. Two to 3 drops of triethylamine was addedto stop the reaction, the solution was added with 5 mL water, thenconcentrated and dried, and the menthyl benzoate produced was extractedwith diethylether. The organic phase was analyzed with ¹H NMR and it wasfound that the menthyl benzoate showed a high yield of 79%. The samereaction as mentioned above was conducted, except for the use ofscandium (III) triflate [Sc(OTf)₃] as a conventionally known Lewis acidcatalyst, instead of the scandium (III)pentafluorophenylbis(triflyl)methide mentioned above. The yield ofmenthyl benzoate was only 48%. Based on these results, it was found outthat the catalytic activity of the scandium (III)pentafluorophenylbis(triflyl)methide of the present invention is muchmore higher compared to that of the existing Lewis acid catalysts.(Chemical Formula 20)

EXAMPLE 16 Diels-Alder Reaction of Methacrolein

Diels-Alder reaction was conducted to a methacrolein wherein thescandium (III) pentafluorophenylbis(triflyl)methide obtained fromExamples 13 and 14 was used as a Lewis acid catalyst (Chemical formula39). Methacrolein (0.21 mL, 2.6 mmol) and cyclopentadiene (0.56 mL, 6.8mmol) were reacted while stirring in 3 mL dichloromethane at −40° C. for4 hours, under the presence of scandium (III)pentafluorophenylbis(triflyl)methide as 1 mol % of Lewis acid catalyst.Two to 3 drops of triethylamine was added to stop the reaction, 5 mL ofwater was added and the 5-norbornene-2-aldehyde produced was extractedwith pentane. After concentration and drying, the crude product wasanalyzed with ¹H NMR and it was found that the 5-norbornene-2-aldehydeshowed a high yield of 95% (88% exo). The same reaction as mentionedabove was conducted, except for the use of scandium (III) triflate[Sc(OTf)₃] as a conventionally known Lewis acid catalyst, instead of thescandium (III) pentafluorophenylbis(triflyl)methide mentioned above. The5-norbornene-2-aldehyde was hardly synthesized. Subsequently, 2 mol % ofthis scandium (III) triflate was used, and the yield of the5-norbornene-2-aldehyde was 97% (89% exo). Based on these results, itwas found out that the catalytic activity of the scandium (III)pentafluorophenylbis(triflyl)methide of the present invention is muchmore higher compared to that of the existing Lewis acid catalysts.(Chemical Formula 21)

As can be seen from the Examples 5 and 9 and Examples 7 and 8 mentionedabove, alkyl lithium generates a nucleophilic substitution reactionspecifically to the para position ofpentafluorophenylbis(triflyl)methane, whereas a nucleophilicsubstitution reaction is generated selectively at the 4′ position whenreacted with{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane.Further, it was found out that as a nucleophilic reactant, not onlylimited to alkyl anion such as alkyl lithium and the like, alkoxy anionalso shows the same reactivity. Moreover, as can be seen from thestructural formula shown below and the pKa value (acetic acid)represented by the numeric value below the formula, when the paraposition of pentafluorophenylbis(triflyl)methane is substituted by anelectron-donating group such as the alkyl group or the alkoxy group, itsacidity decreases. However, when the same substituent was introduced tothe 4′ position of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane,its acidity did not decrease. This fact reveals that the super strongacidity of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane canbe maintained even when it is supported on a resin or the like, with theuse of the nucleophilic substitution reaction to the 4′ position of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane. Itshows that the{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane isvery usuful as a synthesis material for various organic materials andacid catalysts with the use of super strong acidity.

Industrial Applicability

An arylbis(triflyl)methane having strong acidity can be producedefficiently and easily by the method for production according to thepresent invention. Since the pentafluorophenylbis(triflyl)methane andthe like of the present invention are organic acids that are strongerthan TfOH, their use as a novel type of conjugate base of protonic acidor metallic salt is expected. Moreover, since various types of arylgroup can be introduced for an aryl group of arylbis(triflyl)methane, awide application to asymmetric catalyst, functional material and thelike is possible.

Further, the metallic arylbis(perfluoroalkylsulfonyl)methide such asscandium (III) pentafluorophenylbis(triflyl)methide and the like of thepresent invention shows a much better catalytic activity compared tothat of the existing Lewis acid catalysts, and an organic compound canbe easily synthesized at a high yield. The aryl group of metallicarylbis(perfluoroalkylsulfonyl)methide of the present invention can beintroduced with various types of aryl group, and therefore, a wideapplication to asymmetric catalyst, functional material and the like isexpected.

1. An arylbis(perfluoroalkylsulfonyl)methane represented by thefollowing general formula [1]

(wherein R¹ shows a substituted or unsubstituted aryl group (however,phenyl group is excluded), Rf¹ and Rf² are independent to each other andshow a perfluoroalkyl group).
 2. Thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [1] according to claim 1, wherein R¹ is a naphthyl group, a2,4,6-trimethylphenyl group, a 4-(trifluoromethyl)phenyl group, a3,5-bis(trifluoromethyl)phenyl group, a pentafluorophenyl group or aperfluorobiphenyl group.
 3. The arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [1] according to claim 1, wherein Rf¹and Rf² are both a trifluoromethyl group.
 4. Apentafluorophenylbis(trifluoromethylsulfonyl)methane represented byformula [2]

or a para position substituent thereof.
 5. A{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methanerepresented by formula [3]

or a 4′ position substituent thereof.
 6. A method for producing anarylbis(perfluoroalkylsulfonyl)methane represented by general formula[4]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group),whereinan aryl halomethane is reacted with a perfluoroalkyl sulfinate, anarylmethylperfluoroalkylsulfone produced is reacted with a deprotonationagent comprised of an organic metal or a metallic salt, and a metallicsalt of arylmethylperfluoroalkylsulfone obtained is reacted with aperfluoroalkyl sulfonic acid anhydride.
 7. The method for producing thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] according to claim 6, wherein the aryl halomethane isreacted with the perfluoroalkyl sulfinate by heating under reflux usinga solvent with or without the presence of a catalyst.
 8. The method forproducing the arylbis(perfluoroalkylsulfonyl)methane represented by thegeneral formula [4] according to claim 7, wherein a tetrabutyl ammoniumiodide is used as the catalyst.
 9. The method for producing thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] according to claim 7, wherein a propionitrile is used as thesolvent.
 10. The method for producing thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] according to claim 6, wherein a deprotonation agentcomprised of an organic metal or a metallic salt having an equivalentweight of 1.7 to 2.4 is reacted to the arylmethylperfluoroalkylsulfone.11. The method for producing the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [4] according to claim 6, wherein thearyl halomethane is a benzyl bromide, a 2-bromomethylnaphthalene, a1-chloromethylnaphthalene, a 2,4,6-trimethylphenylmethylchloride, a4-(trifluoromethyl)phenylmethylbromide, a3,5-bis(trifluoromethyl)phenylmethylbromide, apentafluorophenylmethylbromide or a 4-(bromomethyl)perfluorobiphenyl.12. The method for producing the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [4] according to claim 6, wherein theperfluoroalkyl sulfinate is an alkaline metallic salt oftrifluoromethane sulfinic acid.
 13. The method for producing thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] according to claim 6, wherein the metallic salt ofarylmethylperfluoroalkylsulfone is a lithium salt or a magnesium salt ofarylmethylperfluoroalkylsulfone.
 14. The method for producing thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] according to claim 6, wherein thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] is an arylbis(trifluoromethylsulfonyl)methane represented bygeneral formula [5]

(wherein R² shows a substituted or unsubstituted aryl group).
 15. Themethod for producing the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [4] according to claim 14, whereinthe arylbis(trifluoromethylsulfonyl)methane represented by the generalformula [5] is a pentafluorophenylbis(trifluoromethylsulfonyl)methanerepresented by formula [2].


16. The method for producing the arylbis(perfluoroalkylsulfonyl)methanerepresented by the general formula [4] according to claim 14, whereinthe arylbis(trifluoromethylsulfonyl)methane represented by the generalformula [5] is a{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methanerepresented by formula [3].


17. A metallic salt of arylbis(perfluoroalkylsulfonyl)methanerepresented by general formula [6]

(wherein R² shows a substituted or unsubstituted aryl group (however,phenyl group is excluded), Rf¹ and Rf² are independent to each other andshow a perfluoroalkyl group, M shows any one of the elements selectedfrom alkaline metallic element, alkaline earth metallic element,transition metallic element, boron, silicon, aluminum, tin, zinc orbismuth, n shows a numeric value equal to the valence of M element). 18.The metallic salt of arylbis(perfluoroalkylsulfonyl) methane accordingto claim 17, wherein the transition metallic element is any one of themetallic elements selected from scandium, yttrium, lanthanoid, copper,silver, titanium, zirconium or hafnium.
 19. The metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 17, whereinRf¹ and Rf² are both a trifluoromethyl group.
 20. The metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 17, wherein R²is a phenyl group, a naphthyl group, a 2,4,6-trimethylphenyl group, a4-(trifluoromethyl)phenyl group, a 3,5-bis(trifluoromethyl)phenyl group,a pentafluorophenyl group or a perfluorobiphenyl group.
 21. The metallicsalt of arylbis(perfluoroalkylsulfonyl)methane according to claim 17,wherein the metallic salt of arylbis(perfluoroalkylsulfonyl)methane is ametallic salt of phenylbis(triflyl)methane, a metallic salt of2-naphthylbis(triflyl)methane, a metallic salt of1-naphthylbis(triflyl)methane, a metallic salt of2,4,6-trimethylphenylbis(triflyl)methane, a metallic salt of4-(trifluoromethyl)phenylbis(triflyl)methane, a metallic salt of3,5-bis(trifluoromethyl)phenylbis(triflyl)methane, a metallic salt ofpentafluorophenylbis(triflyl)methane or a metallic salt of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane.22. The metallic salt of arylbis(perfluoroalkylsulfonyl)methaneaccording to claim 21, wherein the metallic salt ofpentafluorophenylbis(triflyl)methane is a scandium (III)pentafluorophenylbis(triflyl)methide or a lithiumpentafluorophenylbis(triflyl)methide.
 23. The metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 21, whereinthe metallic salt of{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methane isa scandium (III){4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methide ora lithium{4-(pentafluorophenyl)-2,3,5,6-tetrafluorophenyl}bis(triflyl)methide.24. A method for producing a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane, wherein the method is a methodfor producing a metallic salt of arylbis(perfluoroalkylsulfonyl)methanerepresented by general formula [6]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf2 are independent to each other and show a perfluoroalkyl group, M showsany one of the elements selected from alkaline metallic element,alkaline earth metallic element, transition metallic element, boron,silicon, aluminum, tin, zinc or bismuth, n shows a numeric value equalto the valence of M element) wherein anarylbis(perfluoroalkylsulfonyl)methane represented by general formula[4]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group) isneutralized with a hydroxide of a metal.
 25. The method for producingthe metallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 24, wherein the hydroxide of the metal is a hydroxide of a metalselected from alkaline metal or alkaline earth metal.
 26. The method forproducing the metallic salt of arylbis(perfluoroalkylsulfonyl)methaneaccording to claim 24, wherein thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] is used, which is obtained by reacting an aryl halomethanewith a perfluoroalkyl sulfinate, followed by reacting anarylmethylperfluoroalkylsulfone produced with a deprotonation agentcomprised of an organic metal or an metallic salt, and a metallic saltof arylmethylperfluoroalkylsulfone obtained is reacted with aperfluoroalkyl sulfonic acid anhydride.
 27. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 26, wherein the aryl halomethane is reacted with theperfluoroalkyl sulfinate by heating under reflux using a solvent with orwithout the presence of a catalyst.
 28. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 27, wherein a tetrabutyl ammonium iodide is used as the catalyst.29. The method for producing the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 27, wherein apropionitrile is used as the solvent.
 30. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 26, wherein the perfluoroalkyl sulfinate is an alkaline metallicsalt of trifluoromethane sulfinic acid.
 31. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 26, wherein the metallic salt of arylmethylperfluoroalkylsulfoneis a lithium salt or a magnesium salt ofarylmethylperfluoroalkylsulfone.
 32. A method for producing a metallicsalt of arylbis(perfluoroalkylsulfonyl)methane, wherein the method is amethod for producing a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[6],

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group, M showsany one of the elements selected from alkaline metallic element,alkaline earth metallic element, transition metallic element, boron,silicon, aluminum, tin, zinc or bismuth, n shows a numeric value equalto the valence of M element) wherein anarylbis(perfluoroalkylsulfonyl)methane represented by general formula[4]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group) isreacted with a salt or an oxide of transition metal by heating underreflux.
 33. The method for producing the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 32, whereinthe salt or the oxide of transition metal is a lanthanoid metallic saltor a scandium oxide.
 34. The method for producing the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 32, whereinthe arylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] is used, which is obtained by reacting an aryl halomethanewith a perfluoroalkyl sulfinate, followed by reacting anarylmethylperfluoroalkylsulfone produced with a deprotonation agentcomprised of an organic metal or a metallic salt, and a metallic salt ofarylmethylperfluoroalkylsulfone obtained is reacted with aperfluoroalkyl sulfonic acid anhydride.
 35. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 34, wherein the aryl halomethane is reacted with theperfluoroalkyl sulfinate by heating under reflux using a solvent with orwithout the presence of a catalyst.
 36. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 35, wherein a tetrabutyl ammonium iodide is used as the catalyst.37. The method for producing the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 35, wherein apropionitrile is used as the solvent.
 38. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 34, wherein the perfluoroalkyl sulfinate is an alkaline metallicsalt of trifluoromethane sulfinic acid.
 39. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 34, wherein the metallic salt of arylmethylperfluoroalkylsulfoneis a lithium salt or a magnesium salt ofarylmethylperfluoroalkylsulfone.
 40. A method for producing a metallicsalt of arylbis(perfluoroalkylsulfonyl)methane, wherein the method is amethod for producing a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[6]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group, M showsany one of the elements selected from alkaline metallic element,alkaline earth metallic element, transition metallic element, boron,silicon, aluminum, tin, zinc or bismuth, n shows a numeric value equalto the valence of M element) wherein a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[4]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group) isreacted with a halide of a metal having different metal species.
 41. Themethod for producing the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 40, whereinthe metallic salt of arylbis(perfluoroalkylsulfonyl)methane representedby the general formula [6] is a silver salt ofarylbis(perfluoroalkylsulfonyl)methane.
 42. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 40, wherein the arylbis(perfluoroalkylsulfonyl)methane representedby the general formula [4] is used, which is obtained by reacting anaryl halomethane with a perfluoroalkyl sulfinate, followed by reactingan arylmethylperfluoroalkylsulfone produced with a deprotonation agentcomprised of an organic metal or a metallic salt, and a metallic salt ofarylmethylperfluoroalkylsulfone obtained is reacted with aperfluoroalkyl sulfonic acid anhydride.
 43. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 42, wherein the aryl halomethane is reacted with theperfluoroalkyl sulfinate by heating under reflux using a solvent with orwithout the presence of a catalyst.
 44. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 43, wherein a tetrabutyl ammonium iodide is used as the catalyst.45. The method for producing the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 43, wherein apropionitrile is used as the solvent.
 46. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 42, wherein the perfluoroalkyl sulfinate is an alkaline metallicsalt of trifluoromethane sulfinic acid.
 47. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 42, wherein the metallic salt of arylmethylperfluoroalkylsulfoneis a lithium salt or a magnesium salt ofarylmethylperfluoroalkylsulfone.
 48. A method for producing a metallicsalt of arylbis(perfluoroalkylsulfonyl)methane, wherein the method is amethod for producing a metallic salt ofarylbis(perfluoroalkylsulfonyl)methane represented by general formula[6]

(wherein R² shows a substituted or unsubstituted aryl group (however,phenyl group is excluded), Rf¹and Rf² are independent to each other andshow a perfluoroalkyl group, M shows any one of the elements selectedfrom alkaline metallic element, alkaline earth metallic element,transition metallic element, boron, silicon, aluminum, tin, zinc orbismuth, n shows a numeric value equal to the valence of M element)wherein an arylbis(perfluoroalkylsulfonyl)methane represented by generalformula [4]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group) isreacted with a silver carbonate under shade.
 49. The method forproducing the metallic salt of arylbis(perfluoroalkylsulfonyl)methaneaccording to claim 48, wherein thearylbis(perfluoroalkylsulfonyl)methane represented by the generalformula [4] is used, which is obtained by reacting an aryl halomethanewith a perfluoroalkyl sulfinate, followed by reacting anarylmethylperfluoroalkylsulfone produced with a deprotonation agentcomprised of an organic metal or a metallic salt, and a metallic salt ofarylmethylperfluoroalkylsulfone obtained is reacted with aperfluoroalkyl sulfonic acid anhydride.
 50. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 49, wherein the aryl halomethane is reacted with theperfluoroalkyl sulfinate by heating under reflux using a solvent with orwithout the presence of a catalyst.
 51. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 50, wherein a tetrabutyl ammonium iodide is used as the catalyst.52. The method for producing the metallic salt ofarylbis(perfluoroalkylsulfonyl)methane according to claim 50, wherein apropionitrile is used as the solvent.
 53. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 49, wherein the perfluoroalkyl sulfinate is an alkaline metallicsalt of trifluoromethane sulfinic acid.
 54. The method for producing themetallic salt of arylbis(perfluoroalkylsulfonyl)methane according toclaim 49, wherein the metallic salt of arylmethylperfluoroalkylsulfoneis a lithium salt or a magnesium salt ofarylmethylperfluoroalkylsulfone.
 55. A catalyst having a metallic saltof arylbis(perfluoroalkylsulfonyl)methane represented by general formula[6]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group, M showsany one of the elements selected from alkaline metallic element,alkaline earth metallic element, transition metallic element, boron,silicon, aluminum, tin, zinc or bismuth, n shows a numeric value equalto the valence of M element) as an active ingredient.
 56. The catalystaccording to claim 55, wherein the catalyst is a Lewis acid catalyst.57. A method for synthesizing an organic compound wherein the method isa method for synthesizing an organic compound by using a catalyst havinga metallic salt of arylbis(perfluoroalkylsulfonyl)methane represented bygeneral formula [6]

(wherein R² shows a substituted or unsubstituted aryl group, Rf¹ and Rf²are independent to each other and show a perfluoroalkyl group, M showsany one of the elements selected from alkaline metallic element,alkaline earth metallic element, transition metallic element, boron,silicon, aluminum, tin, zinc or bismuth, n shows a numeric value equalto the valence of M element) as an active ingredient, and catalyticreaction is conducted under the presence of said catalyst in a solvent.58. The method for synthesizing an organic compound according to claim57, wherein the catalytic reaction is a benzoylation reaction, aDiels-Alder reaction, an aldol-type reaction, a Friedel-Crafts reaction,a Mannich reaction, a glycosilation reaction, an esterificationreaction, an ene reaction, a cationic polymerization reaction or anallylation reaction.